Coating composition containing N-substituted (meth)acrylamide

Abstract

The objective is to provide a coating composition that exhibits excellent wettability to various substrates, such as organic substrates, inorganic substrates, and organic-inorganic composite materials, having a wide range of polarities from low to high polarity, and that provides a cured product with high transparency, curability, and excellent water resistance upon curing. [Solution] A polymerizable composition containing 1 to 90% by weight of N-substituted (meth)acrylamide (A) represented by general formula [1] and 1 to 99% by weight of monofunctional monomers other than (A), and a coating composition containing a polymer of the polymerizable composition. JPEG2026074100000017.jpg3077 (in the formula, R 1 R represents a hydrogen atom or a methyl group. 2 and R 3 This indicates a saturated ring with six or more members formed by these atoms together with the supporting nitrogen atoms.

Description

[Technical Field]

[0001] The present invention relates to a coating agent composition containing N-substituted (meth)acrylamide. [Background technology]

[0002] In recent years, N-substituted (meth)acrylamides have been widely used as raw material monomers for adhesives, adhesives for optical components, active energy curable adhesives for polarizing plates, inkjet inks, resin compositions for stereolithography, encapsulants for semiconductors and electronic materials, and coatings for glass and resin molded products (Patent Documents 1-4). In particular, they have been reported to be frequently used as a substitute for (meth)acrylic acid because of their high cohesive force of the amide group, excellent adhesion to various substrates, and non-corrosiveness to metals or metal oxides (Patent Documents 5-7). However, many general-purpose N-substituted (meth)acrylamides are hydrophilic monomers soluble in water, and it has been pointed out that their water resistance is insufficient depending on their content and the intended use of the resulting molded product.

[0003] Furthermore, while N-substituted (meth)acrylamide is commonly used as a component of active energy ray curable resins, no method has yet been proposed for improving its water resistance when incorporated into long-life products such as electronic and optical materials. [Prior art documents] [Patent Documents]

[0004] [Patent Document 1] Japanese Patent Publication No. 2008-287207 [Patent Document 2] Japanese Patent Publication No. 2011-122013 [Patent Document 3] Japanese Patent Publication No. 2001-310918 [Patent Document 4] Japanese Patent Publication No. 2010-155889 [Patent Document 5] Japanese Patent Publication No. 2011-137181 [Patent Document 6] Japanese Patent Publication No. 2010-235646 [Patent Document 7] Japanese Patent Publication No. 2013-256552 [Overview of the project] [Problems that the invention aims to solve]

[0005] The first objective of the present invention is to provide a polymerizable composition and polymers of the polymerizable composition that can provide a cured product having excellent wettability to various substrates such as organic substrates, inorganic substrates, and organic-inorganic composite materials having a wide range of polarities from low to high polarity, high transparency, curability, and excellent water resistance upon curing. The second objective is to provide an adhesive composition containing the polymerizable composition and / or its polymers that has adhesion and tackiness to various substrates, high transparency, water resistance, stain resistance, yellowing resistance, and durability, and a laminate of an adhesive layer made of the adhesive composition and various substrates. Furthermore, a third objective of the present invention is to provide an adhesive composition for bonding the same or different materials containing the polymerizable composition and / or its polymer, having high adhesion, impact resistance and water resistance to various substrates; a coating agent composition having high wettability and adhesion to various substrates and exhibiting high surface hardness and water resistance upon curing; a hair cosmetic having moisture resistance, smoothness, resistance to stickiness, good texture and stability over time; an oil-in-water emulsion cosmetic composition that does not cause skin irritation and has excellent emulsification stability, feel and stability over time; an ink having high adhesion to various substrates, excellent printing properties such as pigment dispersibility, surface drying properties, discharge stability and clarity, and high curability, resistance to yellowing and water resistance; and a three-dimensional molding ink composition that can accurately mold three-dimensional objects with high strength, heat resistance and water resistance, and excellent resistance to curing shrinkage. [Means for solving the problem]

[0006] In view of the above, after diligent study, the present inventors have found that a polymerizable composition containing a specific structure of amphiphilic N-substituted (meth)acrylamide, having at least one chain-like or cyclic hydrocarbon group with 6 or more carbon atoms as a hydrophobic group and a (meth)acrylamide group as a hydrophilic group, can solve the above problems, and have completed the present invention.

[0007] In other words, the present invention is (1) A polymerizable composition containing N-substituted (meth)acrylamide (A) represented by general formula [1], [ka] (In the formula, R 1 R represents a hydrogen atom or a methyl group. 2 and R 3 One of them represents a chain hydrocarbon group having 6 or more carbon atoms or a cyclic hydrocarbon group having 6 or more carbon atoms, and the other represents a hydrogen atom, a chain hydrocarbon group having 1 or more carbon atoms or a cyclic hydrocarbon group having 3 or more carbon atoms, R 2 and R 3 This includes those that, together with the supporting nitrogen atoms, form a saturated ring with six or more members. (2) N-substituted (meth)acrylamide (A) is N-monosubstituted (meth)acrylamide and N,N-disubstituted (meth)acrylamide, and has one or more structures as substituents selected from chain saturated and unsaturated structures having 6 or more carbon atoms and 36 or less carbon atoms, and cyclic saturated and unsaturated structures, as described in (1) above, (3) The polymerizable composition according to (1) or (2) above, wherein the saturated water absorption rate of the cured product is 10% or less. (4) The surface tension of N-substituted (meth)acrylamide (A) is 24.0 to 46.0 mN·m -1 The polymerizable composition described in any one of the above items (1) to (3), (5) The polymerizable composition according to any one of the above (1) to (4), wherein the content of N-substituted (meth)acrylamide (A) relative to the entire polymerizable composition is 1% by weight or more. (6) A polymer obtained by polymerizing any one of the polymerizable compositions described in (1) to (5) above by active energy rays and / or heat. (7) A polymerizable composition according to any one of (1) to (5) above, further comprising one or more selected from a polymerization initiator, a compound having an unsaturated bond (excluding N-substituted (meth)acrylamide (A) and polymers using the same), a non-polymerizable oligomer and a non-polymerizable polymer (excluding polymers using N-substituted (meth)acrylamide (A)), and the polymer described in (6) above. (8) A polymerizable composition according to any one of items (1) to (5) and (7) above, or a polymer according to item (6) above, or an adhesive composition containing a polymerizable composition according to any one of items (1) to (5) and (7) above, or a polymer according to item (6) above, and a crosslinking agent. (9) A laminate comprising an adhesive layer made of the adhesive composition described in (8) above and an organic and / or inorganic substrate, wherein the surface tension of the organic and / or inorganic substrate is 22.6 to 59.0 mN·m-1. (10) A polymerizable composition according to any one of items (1) to (5) and (7) above, or an adhesive composition containing the polymer and crosslinking agent according to item (6) above. (11) The absolute difference in surface tension between two dissimilar adherends containing the polymerizable composition described in any one of items (1) to (5) and (7) above, or the polymer and crosslinking agent described in item (6) above, is 37.0 mN·m -1 The adhesive composition is as follows: (12) A cosmetic composition containing a polymerizable composition according to any one of items (1) to (5) and (7) above, or a polymer according to item (6) above. (13) A polymerizable composition according to any one of items (1) to (5) and (7) above, or a polymer according to item (6) above, or a coating composition containing a polymerizable composition according to any one of items (1) to (5) and (7) above, or a polymer according to item (6) above, and a crosslinking agent. (14) A polymerizable composition according to any one of items (1) to (5) and (7) above, or a polymer according to item (6) above, or an ink composition containing a polymerizable composition according to any one of items (1) to (5) and (7) above, or a polymer according to item (6) above, and a crosslinking agent. (15) A polymerizable composition described in any one of items (1) to (5) and (7) above, or a polymer described in item (6) above, or an ink composition for use in three-dimensional molding containing a polymerizable composition described in any one of items (1) to (5) and (7) above, or a polymer described in item (6) above, and a crosslinking agent. This provides... [Effects of the Invention]

[0008] According to the present invention, a polymerizable composition containing N-substituted (meth)acrylamide (A) of a specific structure can be obtained, due to the well-balanced amphiphilicity of N-substituted (meth)acrylamide (A), which provides high transparency and good curability, while exhibiting excellent wettability to various substrates having a wide range of polarities from low to high, including organic substrates, inorganic substrates, and organic-inorganic hybrid substrates. Polymers of the polymerizable composition can also be obtained. By containing the obtained polymerizable composition and / or its polymers, an adhesive composition can be provided that exhibits adhesion and tackiness to various substrates, and has high transparency, stain resistance, yellowing resistance, and durability, as well as a laminate of an adhesive layer made of the adhesive composition and various substrates. Furthermore, the present invention provides adhesive compositions for homogeneous or heterogeneous materials having high adhesion, impact resistance and water resistance to various substrates, hair cosmetics having moisture resistance, smoothness, resistance to stickiness, good texture and long-term stability, oil-in-water emulsion cosmetic compositions that do not exhibit skin irritation and have excellent emulsification stability, feel and long-term stability, coating agents having high wettability and adhesion to various substrates and exhibiting high surface hardness and water resistance upon curing, inks having high adhesion to various substrates, excellent printing characteristics such as pigment dispersibility, surface drying properties, discharge stability and clarity, high curability and resistance to yellowing, and ink compositions for three-dimensional molding that can accurately mold three-dimensional objects with high strength, heat resistance and water resistance, and excellent resistance to curing shrinkage.

Mode for Carrying Out the Invention

[0009] The first embodiment of the present invention is a polymerizable composition. The second embodiment is a polymer obtained by polymerizing the polymerizable composition of the first embodiment with active energy rays and / or heat. The third embodiment is a polymerizable composition further containing one or more selected from a polymerization initiator, a compound having an unsaturated bond (excluding N-substituted (meth)acrylamide (A) and a polymer using the same), a non-polymerizable oligomer, and a non-polymerizable polymer (excluding a polymer using N-substituted (meth)acrylamide (A)) of the polymerizable composition of the first embodiment, and the polymer of the second embodiment. The fourth embodiment is a polymerizable composition further containing one or more selected from a polymerization initiator, a compound having an unsaturated bond (excluding N-substituted (meth)acrylamide (A) and a polymer using the same), a non-polymerizable oligomer, and a non-polymerizable polymer (excluding a polymer using N-substituted (meth)acrylamide (A)) of the polymer of the second embodiment, and a crosslinking agent having two or more reactive functional groups in the molecule (excluding a compound having two or more unsaturated bonds in the molecule). Hereinafter, the first to fourth embodiments of the present invention will be described together.

[0010] The polymerizable composition according to the first embodiment of the present invention contains N-substituted (meth)acrylamide (A) represented by the following general formula [1].

[0011]

Chemical formula

[0012] In general formula [1], R 1 represents a hydrogen atom or a methyl group, and one of R 2 and R 3 represents a chain hydrocarbon group having 6 or more carbon atoms or a cyclic hydrocarbon group having 6 or more carbon atoms, and the other represents a hydrogen atom, a chain hydrocarbon group having 1 or more carbon atoms, or a cyclic hydrocarbon group having 3 or more carbon atoms. R 2 and R 3This includes a saturated ring of 6 or more members formed together with nitrogen atoms supporting them. The saturated ring of 6 or more members may or may not contain heteroatoms. Also, R 2 and R 3 The compound may or may not contain a substituent containing a heteroatom, and if it does, the number of heteroatoms is three or less. A heteroatom is an oxygen atom, a sulfur atom, a nitrogen atom, or a boron atom. N-substituted (meth)acrylamides not included in general formula [1] are also called N-substituted (meth)acrylamide (B).

[0013] The polymer according to the second embodiment of the present invention is a polymer obtained by polymerizing the polymerizable composition of the first embodiment by active energy rays and / or heat. The polymer is a soluble polymer that does not have a crosslinking structure, and may be a homopolymer of any one monomer selected from the N-substituted (meth)acrylamide (A), or a copolymer of A obtained by copolymerizing two or more monomers arbitrarily selected from A in any proportion, or a copolymer obtained by copolymerizing one or more monomers arbitrarily selected from A with copolymerizable monomers other than A in any proportion. In the case of a copolymer obtained from N-substituted (meth)acrylamide (A) and monomers other than A, it is preferable that the content of A in the copolymer is 1% by weight or more of the total weight of the copolymer.

[0014] The N-substituted (meth)acrylamide (A) used in the first to fourth embodiments of the present invention (hereinafter also referred to as these embodiments) is amphiphilic, and the hydrophobic substituents that can impart wettability to low-polarity substrates to the molecule include a chain hydrocarbon group having 6 or more carbon atoms, a cyclic hydrocarbon group having 6 or more carbon atoms, and R 2 and R 3The polymerizable composition according to this embodiment contains N-substituted (meth)acrylamide (A), which provides excellent compatibility of each component of the composition, high transparency, and good wettability to various substrates, including organic substrates, inorganic substrates, and organic-inorganic hybrid substrates with a wide range of polarities from low to high. Furthermore, N-substituted (meth)acrylamide (A) exhibits sufficient curability and polymerizability against active energy rays and / or heat, so polymerizable compositions containing it have high curability and polymerizability. Due to the synergistic effect of the good wettability to various substrates with a wide range of polarities and the strong cohesive force between the amide groups, the polymerizable composition containing N-substituted (meth)acrylamide (A) and / or polymers obtained by polymerizing the polymerizable composition (hereinafter also referred to as polymers of the polymerizable composition or polymers) have excellent adhesion to various substrates. Therefore, as a polymerizable composition and / or a molded article of the polymer thereof, an adhesive composition having high tackiness and stain resistance (reworkability), and an adhesive composition having high adhesion, impact resistance and water resistance can be obtained. The polymerizable composition and / or a polymer thereof according to this embodiment can be applied to various uses, such as coating agent compositions, cosmetic compositions, ink compositions, inkjet ink compositions, and ink compositions used in three-dimensional molding, by utilizing the properties of the N-substituted (meth)acrylamide (A) described above.

[0015] In the above general formula [1], R 2 , R 3In the above, the number of carbon atoms in the chain hydrocarbon group or cyclic hydrocarbon group is preferably 8 or more, more preferably 12 or more, and even more preferably 16 or more, from the viewpoint of improving the wettability of the polymerizable composition to low-polarity substrates according to this embodiment. On the other hand, the number of carbon atoms in the chain hydrocarbon group or cyclic hydrocarbon group is not particularly limited, but in order to sufficiently maintain the wettability of the polymerizable composition to high-polarity substrates, that is, from the viewpoint of balancing wettability to low-polarity and high-polarity substrates, it is usually 36 or less, preferably 24 or less, and more preferably 22 or less. Also, in the general formula [1], R 2 and R 3 The number of members in the saturated ring containing nitrogen atoms supporting the polymer is preferably 6 or more and 12 or less, from the viewpoint of balancing the wettability of the polymerizable composition to low-polarity and high-polarity substrates.

[0016] The N-substituted (meth)acrylamide (A) used in this embodiment is either N-monosubstituted (meth)acrylamide or N,N-disubstituted (meth)acrylamide, and as mentioned above, it is preferable that it has one or more substituents selected from chain-like saturated and unsaturated structures and cyclic saturated and unsaturated structures having 6 to 36 carbon atoms. Furthermore, it is more preferable that the N-substituted (meth)acrylamide (A) has at least one substituent having an unsaturated structure. Generally, among aliphatic compounds with the same number of carbon atoms, those with an unsaturated bond in their structure tend to have a lower melting point than those without. As will be described later, if the N-substituted (meth)acrylamide (A) is liquid at room temperature, its content in the polymerizable composition of this embodiment can be adjusted to some extent. Therefore, it is more preferable for the N-substituted (meth)acrylamide (A) to contain one or more substituents having an unsaturated structure, as this has the effect of lowering its melting point.

[0017] The polymerizable composition according to this embodiment preferably has a saturation water absorption rate of 10% or less at room temperature. In this specification, room temperature refers to 5°C to 35°C under atmospheric pressure. The saturation water absorption rate of the cured product is the water absorption rate in the saturated water absorption state and can be calculated by the method described later. Furthermore, it is sufficient to reach the saturated water absorption state, and the method and conditions for reaching that state are not limited. If the saturation water absorption rate of the cured product is 10% or less, it has sufficient water resistance. The lower the saturation water absorption rate, the higher the water resistance of the cured product, so it is more preferable that the saturation water absorption rate of the cured product is 7% or less, and particularly preferable that it is 5% or less.

[0018] The surface tension of N-substituted (meth)acrylamide (A) is 24.0–46.0 mN·m -1 It is preferable that this is the case. In this specification, the surface tension of N-substituted (meth)acrylamide (A) is a calculated value at 23°C obtained by the Meissner method (Chemical Engineering Handbook, Revised 7th Edition, p. 66), and the average error is 3%.

[0019] When the surface tension of N-substituted (meth)acrylamide (A) is within the above numerical range, when a polymerizable composition containing N-substituted (meth)acrylamide (A) is applied to a substrate of different polarities, the molecules can be aligned to match the polarity of the substrate. As a result, it exhibits good wettability to various substrates with a wide range of polarities as described above, and the adhesion of the polymerizable composition and / or molded articles of its polymer, such as adhesive compositions and bonding agents, is also improved. From these viewpoints, the surface tension of N-substituted (meth)acrylamide (A) is 28.0 to 36.0 mN·m -1 It is more preferable that the value be 30.0~33.0 mN·m -1 It is particularly preferable that this be the case.

[0020] The N-substituted (meth)acrylamide (A) is preferably liquid at room temperature. Because the N-substituted (meth)acrylamide (A) is liquid at room temperature, its content in the polymerizable composition according to this embodiment can be adjusted to some extent arbitrarily without the need for heating or other operations, and the transparency of the resulting polymerizable composition is easily maintained. The N-substituted (meth)acrylamide (A) is more preferably liquid at 30°C or below, and even more preferably liquid at 25°C or below. In this specification, "liquid" includes both a fluid liquid state and a non-fluid wax state.

[0021] In the polymerizable composition according to this embodiment, the content of N-substituted (meth)acrylamide (A) is 1% by weight or more, and may be 100% by weight, relative to the total weight of the polymerizable composition. The content of A can be appropriately adjusted according to the specific application of the polymerizable composition. A content of 1% by weight of N-substituted (meth)acrylamide (A) can improve the curability, polymerizability, transparency, and wettability of the polymerizable composition to active energy rays and / or heat, and to achieve a better balance of curability, polymerizability, transparency, and wettability. Therefore, the content of N-substituted (meth)acrylamide (A) is more preferably 5 to 90% by weight, even more preferably 10 to 80% by weight, and particularly preferably 20 to 70% by weight.

[0022] N-substituted (meth)acrylamide (A) has an aliphatic hydrocarbon group having 6 or more carbon atoms that does not contain an unsaturated bond as a substituent, and the aliphatic hydrocarbon group may be linear, branched, or cyclic. For example, the following N-substituted (meth)acrylamides are listed: n-hexyl(meth)acrylamide, sec-hexyl(meth)acrylamide, tert-hexyl(meth)acrylamide, n-heptyl(meth)acrylamide, sec-heptyl(meth)acrylamide, tert-heptyl(meth)acrylamide, n-octyl(meth)acrylamide, sec-octyl(meth)acrylamide, tert-octyl(meth)acrylamide, 2-ethylhexyl(meth)acrylamide Rylamide, N,N-di-(2-ethylhexyl)acrylamide, n-nonyl(meth)acrylamide, n-decyl(meth)acrylamide, n-undecyl(meth)acrylamide, n-dodecyl(meth)acrylamide, n-tridecyl(meth)acrylamide, n-trimethyldecyl(meth)acrylamide, n-tetradecyl(meth)acrylamide, n-hexadecyl(meth)acrylamide, stearyl(meth)acrylamide, n-eicosyl(meth)acrylamide, n-docosyl N-(meth)acrylamide, n-tetracosyl(meth)acrylamide, N-cyclohexyl(meth)acrylamide, N,N-dicyclohexyl(meth)acrylamide, N-cyclohexyl-N-methyl(meth)acrylamide, N-cyclohexyl-N-ethyl(meth)acrylamide, N-cyclohexyl-N-propyl(meth)acrylamide, N-cyclohexyl-N-butyl(meth)acrylamide, N-cyclohexyl-N-pentyl(meth)acrylamide, N-cyclohexyl N-N-hexyl(meth)acrylamide, N-phenyl(meth)acrylamide, N-(meth)acryloylpiperidine, N-(meth)acryloyl-2-methylpiperidine, N-(meth)acryloyl-3-methylpiperidine, N-(meth)acryloyl-4-methylpiperidine, N-(meth)acryloyl-2,6-dimethylpiperidine, N-(meth)acryloyl-3,5-dimethylpiperidine, N-(meth)acryloyl-3,3-dimethylpiperidine, N-(meth)acryloyl-4,4-dimethylpiperidine, N-(meth)acryloyl-2,2,6,6-tetramethylpiperidine, N-(meth)acryloyl-2-methyl-5-ethylpiperidine, N-(meth)acryloyl-4-methyl-4-ethylpiperidine, N-(meth)acryloyl-2-ethylpiperidine, N-(meth)acryloyl-3-ethylpiperidine, N-(meth)acryloyl-4-ethylpiperidine, N-(meth)acryloyl-2-propylpiperidine Zin, N-(meth)acryloyl-3-propylpiperidine, N-(meth)acryloyl-4-propylpiperidine, N-(meth)acryloyl-3-isopropylpiperidine, N-(meth)acryloyl-4-isopropylpiperidine, N-(meth)acryloylhexamethyleneimine, N-(meth)acryloyl-2-methylhexamethyleneimine, N-(meth)acryloyl-3-methylhexamethyleneimine, N-(meth)acryloyl -4-methylhexamethyleneimine, N-(meth)acryloyl-2-ethylhexamethyleneimine, N-(meth)acryloyl-3-ethylhexamethyleneimine, N-(meth)acryloyl-4-ethylhexamethyleneimine, N-(meth)acryloyl-3-propylhexamethyleneimine, N-(meth)acryloyl-4-propylhexamethyleneimine, N-(meth)acryloyl-3-isopropylhexamethyleneimine, N-( Meth)acryloyl-4-isopropylhexamethyleneimine, N-(meth)acryloyl-3,5-dimethylhexamethyleneimine, N-(meth)acryloyl-4,4-dimethylhexamethyleneimine, N-(meth)acryloylheptamethyleneimine, N-(meth)acryloyloctamethyleneimine, N-(meth)acryloyldecamethyleneimine, dopamine(meth)acrylamide, 3-(meth)acrylamidephenylboronic acid. Among these, from the perspective of readily available industrial products, n-hexyl(meth)acrylamide, n-octyl(meth)acrylamide, tert-octyl(meth)acrylamide, 2-ethylhexyl(meth)acrylamide, N,N-di-(2-ethylhexyl)acrylamide, n-nonyl(meth)acrylamide, n-decyl(meth)acrylamide, n-dodecyl(meth)acrylamide, n-tridecyl(meth)acrylamide, n-trimethyldecyl(meth)acrylamide, n-tetradecyl(meth)acrylamide, n-hexadecyl(meth)acrylamide, stearyl(meth)acrylamide, N-cyclohexyl(meth)acrylamide, N,N-dicyclohexyl(meth)acrylamide Luamide, N-cyclohexyl-N-methyl(meth)acrylamide, N-(meth)acryloylpiperidine, N-(meth)acryloyl-2-methylpiperidine, N-(meth)acryloyl-4-methylpiperidine, N-(meth)acryloyl-2,6-dimethylpiperidine, N-(meth)acryloyl-3,5-dimethylpiperidine, N-phenyl(meth)acrylamide, dopamine(meth)acrylamide, and 3-(meth)acrylamide phenylboronic acid are preferred.

[0023] N-substituted (meth)acrylamide (A) has an aliphatic hydrocarbon group having 6 or more carbon atoms and containing an unsaturated bond as a substituent, and the aliphatic hydrocarbon group may be linear, branched, or cyclic. Examples of N-substituted (meth)acrylamides include: hexenyl(meth)acrylamide, heptenyl(meth)acrylamide, octenyl(meth)acrylamide, nonenyl(meth)acrylamide, decenyl(meth)acrylamide, undecenyl(meth)acrylamide, dodecenyl(meth)acrylamide, tetradecenyl(meth)acrylamide, hexadecenyl(meth)acrylamide, oleyl(meth)acrylamide, eicosenyl(meth)acrylamide, docosenyl(meth)acrylamide, tetracosenyl(meth)acrylamide, octadecadienyl(meth)acrylamide, eicosadienyl(meth)acrylamide, docosadienyl(meth)acrylamide, tetracosadienyl(meth)acrylamide Dienyl(meth)acrylamide, octadecatrienyl(meth)acrylamide, eicosatrienyl(meth)acrylamide, docosatrienyl(meth)acrylamide, tetracosatrienyl(meth)acrylamide, octadecatetraenyl(meth)acrylamide, eicosatetraenyl(meth)acrylamide, docosatetraenyl(meth)acrylamide, tetracosatetraenyl(meth)acrylamide, octadecapentaenyl(meth)acrylamide, eicosapentaenyl(meth)acrylamide, docosapentaenyl(meth)acrylamide, tetracosapentaenyl(meth)acrylamide, docosahexaenyl(meth)acrylamide, tetracosahexaenyl(meth)acrylamide. Among these, octenyl(meth)acrylamide, nonenyl(meth)acrylamide, undecenyl(meth)acrylamide, and oleyl(meth)acrylamide are preferred from the viewpoint of readily available industrial products.

[0024] The polymerizable composition according to this embodiment may further contain, in addition to N-substituted (meth)acrylamide (A), one or more selected from a polymerization initiator, a compound having an unsaturated bond (excluding N-substituted (meth)acrylamide (A) and polymers using the same), a non-polymerizable oligomer and a non-polymerizable polymer (excluding polymers using N-substituted (meth)acrylamide (A)), and a polymer of the polymerizable composition. If the polymerizable composition further contains a polymerization initiator, the curability and polymerizability to active energy rays and / or heat are further improved, and if it further contains a compound having an unsaturated bond, it can be more suitably used as an adhesive composition, a bonding agent composition, a coating agent composition and various ink compositions. Furthermore, if the polymerizable composition further contains a non-polymerizable oligomer and / or a non-polymerizable polymer, the viscosity of the polymerizable composition and the flexibility of its cured product can be easily adjusted. In particular, when a polymerizable composition further contains its polymer, the adhesive strength of the polymerizable composition or the molded product of its polymer (an adhesive composition) to various substrates, and the adhesive strength of the adhesive composition to various substrates, are improved. Hereinafter, "polymerizable composition" refers to both polymerizable compositions that do not contain their polymer and polymerizable compositions that do contain their polymer.

[0025] Examples of compounds having unsaturated bonds include monofunctional monomers and monofunctional oligomers having one unsaturated bond, polyfunctional monomers or polyfunctional oligomers having two or more unsaturated bonds, and polymerizable polymers having unsaturated bonds. These compounds having unsaturated bonds are not limited to those used in the polymerizable composition, but monofunctional monomers are used to adjust the viscosity of the polymerizable composition to the lower viscosity side, polymerizable polymers are used to adjust the viscosity of the polymerizable composition to the higher viscosity side, and polyfunctional monomers, polyfunctional oligomers, and polymerizable polymers are used to adjust the curability of the polymerizable composition and the crosslinking rate of the resulting cured product. In the polymerizable composition of this embodiment, components other than N-substituted (meth)acrylamide (A) may be added individually or in combination of two or more types. The respective content can be adjusted as appropriate depending on the specific application, but it is preferable that the polymerizable composition contains 1 to 99% by weight of monofunctional monomers, 0.05 to 50% by weight of polyfunctional monomers, 0.05 to 50% by weight of polyfunctional oligomers, 0.01 to 10% by weight of polymerizable or non-polymerizable polymers, and 0.01 to 10% by weight of polymerized products of the polymerizable composition, relative to the total weight of the polymerizable composition. In this specification, homopolymers or copolymers of various monomers with a weight-average molecular weight (Mw) of 1,000 or more and less than 10,000 are classified as oligomers, and those with an Mw of 10,000 or more are classified as polymers.

[0026] Polyfunctional monomers are monomers having two or more unsaturated bonds selected from (meth)acrylate groups, (meth)acrylamide groups, vinyl groups, allyl groups, and maleimide groups in their molecule, and examples include polyfunctional (meth)acrylates and polyfunctional (meth)acrylamides. Generally, polyfunctional monomers with 10 or fewer unsaturated bonds in their molecule are preferably used.

[0027] Examples of polyfunctional (meth)acrylates include ethylene glycol di(meth)acrylate, diethylene glycol di(meth)acrylate, propylene glycol di(meth)acrylate, dipropylene glycol di(meth)acrylate, tripropylene glycol di(meth)acrylate, tetraethylene glycol di(meth)acrylate, ditetraethylene glycol di(meth)acrylate, polyethylene glycol di(meth)acrylate, and polypropylene glycol di(meth)acrylate. Polytetramethylene glycol di(meth)acrylate, butylene glycol di(meth)acrylate, 1,3-butanediol di(meth)acrylate, 1,4-butanediol di(meth)acrylate, neopentyl glycol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, 1,6-hexanediol ethylene oxide modified di(meth)acrylate, 1,7-heptanediol di(meth)acrylate, 1,8-octanediol di(meth)acrylate, 1,9-Nonanediol di(meth)acrylate, Neopentyl glycol hydroxypivalate di(meth)acrylate, Dicyclopentanyl di(meth)acrylate, Caprolactone-modified dicyclopentenyl di(meth)acrylate, Ethylene oxide-modified phosphate di(meth)acrylate, Glycerin di(meth)acrylate, Pentaerythritol tetra(meth)acrylate, Pentaerythritol tri(meth)acrylate, Pentaerythritol di(meth)acrylate, Dipentaerythritol tri(meth)acrylate, Dipenta Erythritol hexa(meth)acrylate, dipentaerythritol penta(meth)acrylate, dipentaerythritol tetra(meth)acrylate, ethylene glycol diglycidyl ether di(meth)acrylate, diethylene glycol diglycidyl ether di(meth)acrylate, diglycidyl phthalate di(meth)acrylate, glycerin polyglycidyl ether poly(meth)acrylate, trimethylolethane tri(meth)acrylate, trimethylolpropane tri(meth)acrylate, tricyclodecane Methanol di(meth)acrylate, ethylene oxide-modified bisphenol A type di(meth)acrylate, propylene oxide-modified bisphenol A type di(meth)acrylate, cyclohexanedimethanol di(meth)acrylate, acrylate ester (dioxane glycol diacrylate), alkoxylated hexanediol di(meth)acrylate, alkoxylated cyclohexanedimethanol di(meth)acrylate, epoxy (meth)acrylate, urethane (meth)acrylate, isocyanurate ethylene oxide-modified di(meth)acrylate Examples include acrylate, isocyanurate ethylene oxide-modified tri(meth)acrylate, tri(meth)acryloyloxyethoxytrimethylolpropane, ethylene oxide-modified dipentaerythritol penta(meth)acrylate, ethylene oxide-modified dipentaerythritol hexa(meth)acrylate, ethylene oxide-modified pentaerythritol tri(meth)acrylate, ethylene oxide-modified pentaerythritol tetra(meth)acrylate, succinate-modified pentaerythritol tri(meth)acrylate, etc.

[0028] Examples of polyfunctional (meth)acrylamides include methylenebis(meth)acrylamide, ethylenebis(meth)acrylamide, diallyl(meth)acrylamide, N-[tris(3-(meth)acrylamidepropoxymethyl)methyl](meth)acrylamide, N,N-bis(2-(meth)acrylamideethyl)(meth)acrylamide, 4,7,10-trioxa-1,13-tridecanbis(meth)acrylamide, and N,N'-1,2-ethandylbis[N-(2-(meth)acrylamideethyl)](meth)acrylamide. These polyfunctional monomers may be used individually or in combination of two or more.

[0029] Monofunctional monomers include monofunctional (meth)acrylates, monofunctional (meth)acrylamides, styrenes, alkoxy group-containing monomers, vinyl group-containing monomers, allyl group-containing monomers, and maleimide group-containing monomers, as well as other radical polymerizable compounds that have a reactive double bond in their molecule.

[0030] Monofunctional (meth)acrylates include, for example, methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, isopropyl (meth)acrylate, n-butyl (meth)acrylate, isobutyl (meth)acrylate, hydroxyethyl (meth)acrylate, tert-butyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, isodecyl (meth)acrylate, lauryl (meth)acrylate, stearyl (meth)acrylate, iso Stearyl (meth)acrylate, Tridecyl (meth)acrylate, Methoxyethyl (meth)acrylate, Ethoxyethyl (meth)acrylate, Propoxyethyl (meth)acrylate, Butoxyethyl (meth)acrylate, Methoxydiethylene glycol (meth)acrylate, Methoxytriethylene glycol (meth)acrylate, Methoxytetraethylene glycol (meth)acrylate, 2-(2-ethoxyethoxy)ethyl acrylate, Phenoxyethyl (meth) Examples include acrylates, phenoxydiethylene glycol (meth)acrylate, phenoxytetraethylene glycol (meth)acrylate, phenoxyhexaethylene glycol (meth)acrylate, methoxydipropylene glycol (meth)acrylate, methoxytripropylene glycol (meth)acrylate, cyclohexyl (meth)acrylate, tert-butylcyclohexyl (meth)acrylate, benzyl (meth)acrylate, dicyclopentanyl (meth)acrylate, dicyclopentenyl (meth)acrylate, bornyl (meth)acrylate, isobornyl (meth)acrylate, tetrahydrofurfuryl acrylate, 2-methyl-2-adamantyl (meth)acrylate, allyl (meth)acrylate, hydroxyethyl (meth)acrylate, hydroxypropyl (meth)acrylate, 2-hydroxybutyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, and hydroxyhexyl (meth)acrylate.

[0031] Examples of monofunctional (meth)acrylamides include N-methyl(meth)acrylamide, N-ethyl(meth)acrylamide, N-isopropyl(meth)acrylamide, N-butyl(meth)acrylamide, N-methoxymethyl(meth)acrylamide, N-ethoxymethyl(meth)acrylamide, N-methoxyethyl(meth)acrylamide, N-ethoxyethyl(meth)acrylamide, Nn-butoxymethyl(meth)acrylamide, N-isobutoxymethyl(meth)acrylamide, N-(2-hydroxyethyl)acrylamide, N-[3-(dimethylamino)]propylacrylamide, N,N-dimethyl(meth)acrylamide, N,N-diethyl(meth)acrylamide, and diacetone(meth)acrylamide. These monofunctional (meth)acrylamides are included in the aforementioned N-substituted (meth)acrylamides (B).

[0032] Examples of vinyl group-containing monomers include N-vinylpyrrolidone, N-vinylcaprolactam, acrylonitrile, vinyl acetate, styrene, and vinyloxazoline. These monofunctional monomers may be used individually or in combination of two or more.

[0033] Examples of monofunctional oligomers, polyfunctional oligomers, and polymerizable polymers include linear and / or branched oligomers and polymers having a backbone such as acrylic, ester, ether, urethane, or amide, and can be classified into urethane-based, epoxy-based, and acrylic-based types based on their main chain structure. When these are classified by weight-average molecular weight (Mw), examples of oligomers consisting of the above-mentioned polyfunctional (meth)acrylate and / or polyfunctional (meth)acrylamide can be given for those with an Mw of 1,000 or more and less than 10,000, while examples of polymerizable polymers with an Mw of 10,000 or more include the following: difunctional polyurethane (meth)acrylate, polyfunctional polyurethane (meth)acrylate, difunctional polyester (meth)acrylate, polyfunctional urethane (meth)acrylate, difunctional polyester (meth)acrylate, polyfunctional polyester (meth)acrylate, difunctional polyether (meth)acrylate, polyfunctional polyether (meth)acrylate, difunctional polyamide (meth)acrylate, polyfunctional poly Amide (meth)acrylate, difunctional poly(meth)acrylic acid ester (meth)acrylate, polyfunctional poly(meth)acrylic acid ester (meth)acrylate, difunctional poly(meth)acrylic acid ester (meth)acrylamide, polyfunctional poly(meth)acrylic acid ester (meth)acrylamide, difunctional poly(meth)acrylamide (meth)acrylate, polyfunctional poly(meth)acrylamide (meth)acrylate, difunctional polystyrene (meth)acrylate, polyfunctional polystyrene (meth)acrylate, difunctional polyacrylonitrile (meth)acrylate, polyfunctional polyacrylonitrile (meth)acrylate, difunctional epoxy acrylate (bisphenol A type), polyfunctional epoxy acrylate (bisphenol A type), etc. These oligomers or polymers may be used individually or in combination of two or more types.

[0034] Furthermore, monofunctional or polyfunctional oligomers are readily available as commercially produced urethane acrylates, such as Mitsubishi Chemical Corporation's UV-3200B, UV-3000B, UV-6640B, UV-3700B, UV-3310B, UV-7000B, Shin-Nakamura Chemical Industry Co., Ltd.'s U-4HA, U-200PA, and Daicel-Scytec Corporation's EBECRYL245, EBEC RYL1259, EBECRYL8210, EBECRYL284, EBECRYL8402, SARTOMER products (product names CN944, CN969, CN9002, CN9029), Negami Kogyo products (product names UN1255, UN-5507), Kyoeisha products (product names AH-600, UA-306I, etc.) can be used, and as UV-curable urethane oligomers, KJ Chemicals products (Quick Cure® 6100, Quick Cure® 7100, Quick Cure® 8100, etc.) can be used.

[0035] The compounds having unsaturated bonds may be monomers or oligomers having unsaturated bonds, and are preferably the various monofunctional monomers, polyfunctional monomers, or oligomers mentioned above. From the viewpoint of obtaining a thermoplastic polymer used for adjusting physical properties such as viscosity, the compounds having unsaturated bonds contained in the polymerizable composition of this embodiment are preferably monofunctional monomers having one unsaturated bond, and from the viewpoint of increasing the cohesive strength of the obtained polymer, monomers that can introduce crosslinking points are particularly preferred. The content of these compounds having unsaturated bonds can be arbitrarily adjusted according to the specific application, but is preferably 1 to 99% by weight in total with respect to the total weight of the polymerizable composition according to this embodiment.

[0036] The monomers that can introduce the aforementioned crosslinking sites are monomers having one or more reactive functional groups in their molecules, and examples include functional group-containing (meth)acrylic monomers such as hydroxyl group-containing (meth)acrylic monomers, carboxyl group-containing (meth)acrylic monomers, amino group-containing (meth)acrylic monomers, acetoacetyl group-containing (meth)acrylic monomers, isocyanate group-containing (meth)acrylic monomers, glycidyl group-containing (meth)acrylic monomers, and oxazoline group-containing vinyl monomers.

[0037] Examples of the hydroxyl group-containing (meth)acrylic monomers include hydroxyalkyl (meth)acrylates such as 2-hydroxyethyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, 5-hydroxypentyl (meth)acrylate, 6-hydroxyhexyl (meth)acrylate, and 8-hydroxyoctyl (meth)acrylate; hydroxyalkyl (meth)acrylamides such as N-hydroxyethyl (meth)acrylamide and N-hydroxypropyl (meth)acrylamide; and other examples such as 2-acryloyloxyethyl 2-hydroxyethyl Examples include primary hydroxyl group-containing (meth)acrylic monomers such as phthalic acid and N-methylol(meth)acrylamide, secondary hydroxyl group-containing (meth)acrylic monomers such as 2-hydroxypropyl(meth)acrylate, 2-hydroxybutyl(meth)acrylate, 2-hydroxy-3-phenoxypropyl(meth)acrylate, 3-chloro-2-hydroxypropyl(meth)acrylate, and 2-hydroxy-3-phenoxypropyl(meth)acrylate, and tertiary hydroxyl group-containing (meth)acrylic monomers such as 2,2-dimethyl-2-hydroxyethyl(meth)acrylate. Among these, hydroxyalkyl(meth)acrylates are preferably used.

[0038] Examples of the carboxyl group-containing (meth)acrylic monomers mentioned above include monocarboxylic acids such as (meth)acrylic acid and crotonic acid, and dicarboxylic acids such as maleic acid, maleic anhydride, fumaric acid, citraconic acid, and itaconic acid. Among these, (meth)acrylic acid is preferably used.

[0039] Examples of the amino group-containing (meth)acrylic monomers include aminoalkyl (meth)acrylates such as N,N-dimethylaminoethyl (meth)acrylate, N,N-dimethylaminopropyl (meth)acrylate, N,N-di-t-butylaminoethyl (meth)acrylate, and N,N-diethylaminoethyl (meth)acrylate, and aminoalkyl (meth)acrylamides such as N,N-dimethylaminoethyl (meth)acrylamide, N,N-diethylaminoethyl (meth)acrylamide, and N,N-dimethylaminopropyl (meth)acrylamide.

[0040] Examples of the acetoacetyl group-containing (meth)acrylic monomer include 2-(acetoacetoxy)ethyl (meth)acrylate.

[0041] Examples of the glycidyl group-containing (meth)acrylic monomers include glycidyl (meth)acrylate, glycidyl (meth)acrylamide, N-hydroxyethyl (meth)acrylamide glycidyl ether, N-methyl-N-hydroxyethyl (meth)acrylamide glycidyl ether, N-ethyl-N-hydroxyethyl (meth)acrylamide glycidyl ether, N-propyl-N-hydroxyethyl (meth)acrylamide glycidyl ether, N-butyl-N-hydroxyethyl (meth)acrylamide glycidyl ether, N-hydroxypropyl (meth)acrylamide glycidyl ether, N-hydroxybutyl (meth)acrylamide glycidyl ether, N-hydroxypentyl (meth)acrylamide glycidyl ether, N-hydroxyhexyl (meth)acrylamide glycidyl ether, N-hydroxyheptyl (meth)acrylamide glycidyl ether, and N-hydroxyoctyl (meth)acrylamide glycidyl ether.

[0042] Examples of the oxazoline group-containing vinyl monomers include 2-vinyl-2-oxazoline, 4-methyl-2-vinyl-2-oxazoline, 5-methyl-2-vinyl-2-oxazoline, 4-ethyl-2-vinyl-2-oxazoline, 5-ethyl-2-vinyl-2-oxazoline, 4,4-dimethyl-2-vinyl-2-oxazoline, 4,4-diethyl-2-vinyl-2-oxazoline, 4,5-dimethyl-2-vinyl-2-oxazoline, 4,5-diethyl-2-vinyl-2-oxazoline, and 2-isopropenyl Examples include 2-2-oxazoline, 4-methyl-2-isopropenyl-2-oxazoline, 5-methyl-2-isopropenyl-2-oxazoline, 4-ethyl-2-isopropenyl-2-oxazoline, 5-ethyl-2-isopropenyl-2-oxazoline, 4,4-dimethyl-2-isopropenyl-2-oxazoline, 4,4-diethyl-2-isopropenyl-2-oxazoline, 4,5-dimethyl-2-isopropenyl-2-oxazoline, and 4,5-diethyl-2-isopropenyl-2-oxazoline. Furthermore, highly reactive 2-vinyl-2-oxazoline, 5-methyl-2-vinyl-2-oxazoline, and 4,4-dimethyl-2-vinyl-2-oxazoline are preferred, with 2-vinyl-2-oxazoline being the most preferred. The monomers that can introduce these crosslinking sites are not limited to one type, but may be used in combination with multiple types.

[0043] In this embodiment, the crosslinking agent is a compound that can introduce a crosslinked structure into the cured product of a polymerizable composition, and includes monomers that can introduce the aforementioned crosslinking points, oligomers and polymers that can introduce multiple crosslinking points obtained by polymerizing them, compounds having two or more reactive functional groups in the molecule, polyfunctional monomers having two or more unsaturated bonds in the molecule, and polymerizable polymers of polyfunctional oligomers. In this embodiment, if the monomer that can introduce crosslinking points is a monofunctional monomer having one or more reactive functional groups in the molecule, it is treated as a monofunctional monomer. The crosslinking methods using a crosslinking agent in this embodiment include: (1) a method of crosslinking a polymerizable composition or its polymer by further incorporating a compound having a functional group (e.g., an isocyanate group or a carboxyl group) that reacts with a reactive functional group (e.g., a hydroxyl group or an amino group) contained in the polymerizable composition or its polymer; (2) a method of crosslinking a polymerizable composition or its polymer by incorporating a polyfunctional monomer, polyfunctional oligomer, or polymerizable polymer and irradiating it with active energy rays; and (3) a method of crosslinking a polymerizable composition or its polymer by incorporating a crosslinking agent such as a polyfunctional monomer, polyfunctional oligomer, polymerizable polymer, or monomer capable of introducing crosslinking sites and irradiating it with active energy rays and / or reacting with the crosslinking agent. Note that crosslinking method (3) is a method that appropriately combines crosslinking methods (1) and (2).

[0044] In the above crosslinking method (1), examples of crosslinking agents (i.e., compounds having functional groups that react with reactive functional groups contained in the polymerizable composition or its polymer) include isocyanate compounds, epoxy compounds, aziridine compounds, compounds having carboxyl groups or oxazoline groups, etc.

[0045] Examples of isocyanate compounds include aromatic isocyanates such as tolylene diisocyanate and xylene diisocyanate, alicyclic isocyanates such as isophorone diisocyanate, and aliphatic isocyanates such as hexamethylene diisocyanate. More specifically, examples of isocyanate compounds include lower aliphatic polyisocyanates such as butylene diisocyanate and hexamethylene diisocyanate; alicyclic isocyanates such as cyclopentylene diisocyanate, cyclohexylene diisocyanate, and isophorone diisocyanate; aromatic diisocyanates such as 2,4-tolylene diisocyanate, 4,4'-diphenylmethane diisocyanate, and xylylene diisocyanate; and isocyanate adducts such as trimethylolpropane / tolylene diisocyanate trimer adduct (manufactured by Tosoh Corporation, trade name: Coronate L), trimethylolpropane / hexamethylene diisocyanate trimer adduct (manufactured by Tosoh Corporation, trade name: Coronate HL), and isocyanurate derivatives of hexamethylene diisocyanate (manufactured by Tosoh Corporation, trade name: Coronate HX). These isocyanate compounds may be used individually or in combination of two or more.

[0046] Examples of epoxy compounds include polyethylene glycol diglycidyl ether, polyglycerol polyglycidyl ether, glycerin diglycidyl ether, diglycidyl ether, trimethylolpropane triglycidyl ether, diglycidylaniline, N,N,N',N'-tetraglycidyl-m-xylenediamine (manufactured by Mitsubishi Gas Chemical Co., Ltd., trade name: TETRAD-X), and 1,3-bis(N,N-diglycidylaminomethyl)cyclohexane (manufactured by Mitsubishi Gas Chemical Co., Ltd., trade name: TETRAD-C). These compounds may be used individually or in combination of two or more.

[0047] Examples of aziridine compounds include commercially available products with trade names HDU, TAZM, and TAZO (all manufactured by Sogo Yakuko Co., Ltd.). These compounds may be used individually or in combination of two or more.

[0048] Compounds having a carboxyl group include aromatic dicarboxylic acids such as phthalic acid, isophthalic acid, 1,4-naphthalenedicarboxylic acid, 2,6-naphthalenedicarboxylic acid, diphenyldicarboxylic acid, diphenoxyethanedicarboxylic acid, diphenyletherdicarboxylic acid, and diphenylsulfondicarboxylic acid; alicyclic dicarboxylic acids such as 1,3-cyclopentanedicarboxylic acid, 1,3-cyclohexanedicarboxylic acid, and 1,4-cyclohexanedicarboxylic acid; aliphatic dicarboxylic acids such as malonic acid, dimethylmalonic acid, succinic acid, 3,3-diethylsuccinic acid, glutaric acid, 2,2-dimethylglutaric acid, adipic acid, 2-methyladipic acid, trimethyladipic acid, pimelic acid, azelaic acid, sebacic acid, and suberic acid; hydroxycarboxyl groups such as glycolic acid, 3-hydroxybutyric acid, 4-hydroxyvaleric acid, hydroxypropionic acid, hydroxycaproic acid, and hydroxybenzoic acid; and compounds having a dicarboxyl group derived from their ester-forming derivatives or their anhydrides. These compounds may be used individually or in combination of two or more.

[0049] Compounds containing an oxazoline group include alkylene bisoxazolines such as tetramethylenebisoxazoline and hexamethylenebisoxazoline, aromatic bisoxazolines such as 1,3-phenylenebis(2-oxazoline) and 1,4-bis(4,5-dihydro-2-oxazolyl)benzene, and oxazoline group-containing compounds such as homopolymers of the aforementioned oxazoline group-containing vinyl monomers and copolymers with compounds having unsaturated bonds. These compounds may be used individually or in combination of two or more.

[0050] The content of the crosslinking agent (i.e., a compound having two or more functional groups in its molecule that react with reactive functional groups contained in the polymerizable composition or its polymer) in crosslinking method (1) can be appropriately selected depending on the balance with the amount and molecular weight of reactive functional groups contained in the polymerizable composition or its polymer, and further depending on the specific application. However, it is usually preferably 0.1 to 15% by weight, more preferably 0.5 to 10% by weight, and particularly preferably 1 to 5% by weight, relative to the total weight of the polymerizable composition. If the content is less than 0.1% by weight, the crosslinking by the crosslinking agent will be insufficient, and if the molded product after the crosslinking reaction is a cured product of an adhesive composition and a tack, sufficient durability may not be obtained, and it may also tend to cause adhesive residue (contamination) in the tack composition. Furthermore, if the molded product after the crosslinking reaction is a cured product of a coating agent, sufficient surface hardness may not be obtained, and if the molded product after the crosslinking reaction is a cured product of a three-dimensional molding ink, i.e., a three-dimensional molded product, it may not be possible to obtain a molded product with sufficient hardness and tensile strength. On the other hand, if the content exceeds 15% by weight, and the molded product after the crosslinking reaction is a cured product of the adhesive composition and the tack composition, the flexibility will decrease, and the adhesion to the substrate will also decrease, making it impossible to obtain sufficient tackiness and adhesive strength. Furthermore, if the molded product after the crosslinking reaction is a cured product of ink for three-dimensional molding, i.e., a three-dimensional molded product, it may not be possible to obtain a molded product with sufficient elongation at break. Note that the crosslinking reaction in crosslinking method (1) may be carried out at room temperature, but it is preferable to carry it out at a temperature of about 40°C to 120°C to promote the reaction.

[0051] In the crosslinking method (2) described above, the crosslinking agent (i.e., polyfunctional monomer, polyfunctional oligomer, or polymerizable polymer) can be one of those described above. In addition, in the crosslinking method (2), irradiation can be performed using various active energy rays described later. When ultraviolet light (UV, UV-LED, etc.) or visible light is used as the active energy ray, it is preferable to use a photopolymerization initiator in combination. When an electron beam (EB) or an energy ray with a shorter wavelength than an electron beam is used as the active energy ray, a high energy can be supplied, so it is not necessary to include a photopolymerization initiator. Furthermore, if the unsaturated bond in the molecule of the polyfunctional monomer, polyfunctional oligomer, or polymerizable polymer is a self-starting functional group such as a maleimide group, allyl ether group, or vinyl ether group, it is not necessary to include a photopolymerization initiator.

[0052] In crosslinking method (2), the content of the crosslinking agent (i.e., polyfunctional monomer, polyfunctional oligomer, or polymerizable polymer) is preferably 0.05 to 50% by weight of the total weight of the polymerizable composition. More preferably, 0.1 to 30% by weight is preferred, and 0.5 to 20% by weight is particularly preferred, from the viewpoint of a good balance between the adhesion of the cured product to various substrates after crosslinking and the hardness and strength of the resulting cured product. If the content is less than 0.05% by weight, the crosslinking by the crosslinking agent will be insufficient, and if the molded product after the crosslinking reaction is an adhesive composition, sufficient durability may not be obtained, and in the adhesive composition, it may tend to cause adhesive residue (contamination). Furthermore, if the molded product after the crosslinking reaction is a cured product of a coating agent, sufficient surface hardness may not be obtained, and if the molded product after the crosslinking reaction is a cured product of an ink for three-dimensional modeling materials, i.e., a three-dimensional object, it may not be possible to obtain an object with sufficient hardness and tensile strength. On the other hand, if the content exceeds 50% by weight, and the molded product after the crosslinking reaction is a cured product of the adhesive composition and the tack composition, shrinkage due to curing, which is characteristic of active energy ray curing, is likely to occur, which tends to cause delamination and cracking. In that case, of course, sufficient tackiness and adhesive strength cannot be obtained. Also, if the molded product after the crosslinking reaction is a cured product of the coating agent, delamination and cracking of the cured film, which is the molded product, are likely to occur due to curing shrinkage. If the molded product after the crosslinking reaction is a three-dimensional object, sufficient elongation at break may not be obtained.

[0053] The content of the crosslinking agent (i.e., polyfunctional monomers, polyfunctional oligomers, or polymerizable polymers, and compounds having two or more reactive functional groups in their molecules) in crosslinking method (3) varies depending on the type of crosslinking agent used. The content of polyfunctional monomers, polyfunctional oligomers, or polymerizable polymers is preferably 0.05 to 30% by weight of the total weight of the polymerizable composition, and the content of compounds having two or more reactive functional groups in their molecules is preferably 0.1 to 10% by weight of the total weight of the polymerizable composition. Furthermore, since polyfunctional monomers, polyfunctional oligomers, polymerizable polymers, and compounds having two or more reactive functional groups in their molecules are used in mixture, the total content of these crosslinking agents is preferably 0.15 to 40% by weight, more preferably 0.2 to 35% by weight, and particularly preferably 0.5 to 30% by weight of the total weight of the polymerizable composition. If the total content is less than 0.15% by weight, crosslinking by the crosslinking agent will be insufficient. If the molded product after the crosslinking reaction is a cured product of an adhesive composition, sufficient durability may not be obtained, and there is a tendency for adhesive residue (contamination) to occur in the adhesive composition. Furthermore, if the molded product after the crosslinking reaction is a cured product of a coating agent, sufficient surface hardness may not be obtained. If the molded product after the crosslinking reaction is a cured product of a 3D printing ink, i.e., a 3D printed object, it may not be possible to obtain a printed object with sufficient hardness and tensile strength. If the total content exceeds 40% by weight, if the molded product after the crosslinking reaction is a cured product of an adhesive composition, flexibility will decrease, adhesion to the substrate will also decrease, and sufficient tackiness and adhesive strength may not be obtained. Furthermore, if the molded product after the crosslinking reaction is a cured product of a 3D printing ink, i.e., a 3D printed object, it may not be possible to obtain a printed object with sufficient elongation at break.

[0054] As described above, the polymerizable composition according to this embodiment may further contain a non-polymerizable oligomer having a weight-average molecular weight (Mw) of 1,000 or more and less than 10,000, and / or a non-polymerizable polymer having an Mw of 10,000 or more. Examples of non-polymerizable oligomers and non-polymerizable polymers include thermoplastic resins, rosin-based resins, or mixtures thereof. Examples of thermoplastic resins include (meth)acrylic resins, cyclic polyolefin resins, cellulose resins, polyester resins, polyurethane resins, polysulfonic acid resins, ABS resins which are copolymers of acrylonitrile, butadiene, and styrene, polycarbonate resins, polyamide resins, and polyimide resins. Examples of rosin-based resins include natural rosins such as gum rosin, and modified rosin resins such as hydrogenated rosin, disproportionated rosin, rosin-modified phenol resins, maleic acid-modified rosin resins, maleated rosin, and esterified gum obtained by modifying natural rosin. These non-polymerizable oligomers and non-polymerizable polymers may be used individually or in combination of two or more types.

[0055] As described above, the polymerizable composition according to this embodiment may further contain a polymerization initiator and / or a compound having an unsaturated bond. In this case, the polymerizable composition has improved curability and polymerizability by active energy rays and / or heat, and can be suitably used as an active energy ray and / or thermosetting adhesive composition, adhesive composition, coating composition, ink composition, etc. For example, as an adhesive composition, an adhesive layer can be formed by applying the polymerizable composition to a separator or various substrates described later, and then curing it with active energy rays. In this specification, polymerization of a polymerizable composition by active energy rays and heat is also referred to as hybrid polymerization. In hybrid polymerization, polymerization may be carried out in the order of active energy rays followed by heat, or in the order of heat followed by active energy rays.

[0056] An active energy ray is defined as an energy ray capable of generating active species by decomposing a compound that generates active species (photopolymerization initiator). Examples of such active energy rays include visible light, ultraviolet light, infrared light, alpha rays, beta rays, gamma rays, X-rays, and electron beams (EB). When an electron beam is used as the active energy ray, a photopolymerization initiator may not be used. On the other hand, when ultraviolet light or visible light is used, it is preferable to use a photopolymerization initiator. Irradiation with an active energy ray is preferably carried out under an inert gas atmosphere such as nitrogen gas or carbon dioxide, or under an atmosphere with reduced oxygen concentration. However, the polymerizable composition according to this embodiment has good curability because it contains N-substituted (meth)acrylamide (A), and can be sufficiently cured even under a normal air atmosphere. The irradiation temperature of the active energy ray is preferably 10°C to 200°C, and the irradiation time is preferably 1 second to 60 minutes.

[0057] The photopolymerization initiator can be any substance that generates radicals when irradiated with ultraviolet light of an appropriate wavelength that can trigger the polymerization reaction, depending on the type of active energy ray reactive component (i.e., a photoradical polymerization initiator). The photopolymerization initiator can be appropriately selected from common types such as acetophenone-based, benzoin-based, thioxanthone-based, etc. Commercially available products include IGM Resins BV's Omnirad 1116, Omnirad 1173, Omnirad 184, Omnirad 369, Omnirad 500, Omnirad 651, Omnirad 754, Omnirad 819, Omnirad 907, Omnirad 1300, Omnirad 1800, Omnirad 1870, Omnirad 2959, Omnirad 4265, Omnirad TPO, etc., and UCB's Yubecryl P36, etc. These photopolymerization initiators may be used individually or in combination of two or more.

[0058] As a photoradical polymerization initiator, there are no particular limitations, and examples include benzoins such as benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin isobutyl ether, and anisole methyl ether; acetophenones such as 4-(2-hydroxyethoxy)phenyl(2-hydroxy-2-propyl)ketone, α-hydroxy-α,α'-dimethylacetophenone, methoxyacetophenone, 2,2'-dimethoxy-2-phenylacetophenone, 2-hydroxy-2-cyclohexylacetophenone, 2,2-diethoxyacetophenone, 2,2-dimethoxy-2-phenylacetophenone, 1-hydroxycyclohexylphenyl ketone, 4-phenoxydichloroacetophenone, and 4-t-butyl-dichloroacetophenone; propiophenones such as 2-hydroxy-2-methylpropiophenone and 2-hydroxy-4'-isopropyl-2-methylpropiophenone; benzophenone; methylben Benzophenones such as zophenone, p-chlorbenzophenone, and p-dimethylaminobenzophenone; thioxanthones such as thioxanthone, 2-chlorthioxanthone, 2-tilthioxanthone, 2-isopropylthioxanthone, 2,4-dichlorothioxanthone, 2,4-diethylthioxanthone, 2,4-diisopropylthioxanthone, and dodecylthioxanthone; bis(2,4,6-trimethylbenzoyl)phenylphosphine oxide, 2,4,6-trimethylbenzoyl Examples include acylphosphine oxides such as tylbenzoyldiphenylphosphine oxide, bis(2,4,6-trimethylbenzoyl)-2,4-di-n-butoxyphenylphosphine oxide, and bis(2,6-dimethoxybenzoyl)-2,4,4-trimethylpentylphenylphosphine oxide, as well as benzyl, dibenzosverone, and α-acyloxime esters. One photoradical polymerization initiator may be used alone, or two or more may be used in combination.

[0059] The content of these photopolymerization initiators is typically 0.1 to 10% by weight, preferably 0.1 to 5% by weight, and more preferably 0.5 to 3% by weight, based on the total weight of the polymerizable composition according to this embodiment. If the content of the photopolymerization initiator is less than 0.1% by weight, sufficient curability cannot be obtained, and if it exceeds 10% by weight, the performance of the cured product, such as its strength, may decrease.

[0060] The polymerizable composition according to this embodiment can be thermally polymerized by known methods in the presence of a thermal polymerization initiator, such as emulsion polymerization, solution polymerization, suspension polymerization, and bulk polymerization. When using solution polymerization, there are no particular restrictions on the solvent that can be used as long as it dissolves the polymer obtained by polymerization. Examples include aromatic hydrocarbons such as benzene, toluene, ethylbenzene, and xylene; aliphatic hydrocarbons such as hexane, heptane, octane, decane, and cyclohexane; esters such as ethyl acetate, butyl acetate, and 2-hydroxyethyl acetate; aliphatic alcohols such as ethyl alcohol, n-propyl alcohol, and isopropyl alcohol; ketones such as acetone, methyl ethyl ketone, and methyl isobutyl ketone; acetonitrile; and N,N-dimethylformamide. These solvents may be used individually or in combination of two or more. In particular, from the viewpoint of ease of removal when forming molded articles, the use of low-boiling point solvents such as ethyl acetate, methyl ethyl ketone, and acetone is preferred. The temperature and time of thermal polymerization vary depending on the thermal polymerization method and the thermal polymerization initiator used, but are usually calculated from the half-life of the initiator. The temperature is usually preferably 60°C to 120°C, and the time is usually preferably 2 to 20 hours, with 5 to 10 hours being more preferable.

[0061] Examples of thermal polymerization initiators include thermal radical polymerization initiators, such as azo compound catalysts like azobisisobutyronitrile, azobisvaleronitrile, and azobis(isobutyrate)dimethyl; peroxide catalysts like benzoyl peroxide and hydrogen peroxide; and persulfate catalysts like ammonium persulfate and sodium persulfate. The content of the thermal polymerization initiator is approximately 0.01 to 10% by weight relative to the total weight of the polymerizable composition. Furthermore, conventional radical polymerization techniques, such as adjusting the molecular weight with a chain transfer agent, can be applied.

[0062] As described above, polymers obtained by polymerizing the polymerizable composition according to this embodiment by the various methods described above may be further contained as components of the polymerizable composition. The molecular weight of the polymer of the polymerizable composition according to this embodiment is usually 1,000 to 2,000,000 in weight-average molecular weight (Mw), preferably 5,000 to 1,000,000, and particularly preferably 10,000 to 500,000. If Mw is within the range of 1,000 to 2,000,000, the solution viscosity when the polymer is dissolved in a solvent or a general-purpose low-viscosity monomer is neither too high nor too low, making it suitable for handling and resulting in high processing accuracy for adhesive sheets, coatings, three-dimensional molded objects, etc. When the polymer is diluted with ethyl acetate so that the solid content is 30%, the solution viscosity at 25°C is usually 10 to 100,000 mPa·s, preferably 500 to 10,000 mPa·s, and more preferably 1,000 to 5,000 mPa·s. Viscosity can be measured in accordance with the cone-plate viscometer method specified in JIS K5600-2-3.

[0063] A fifth embodiment of the present invention is an adhesive composition (hereinafter also referred to as "adhesive"). The adhesive composition according to the fifth embodiment contains a polymerizable composition or polymer thereof according to the first to fourth embodiments, or the polymerizable composition or polymer thereof and a crosslinking agent. The polymerizable composition or polymer thereof according to the first to fourth embodiments contains N-substituted (meth)acrylamide (A), and therefore has sufficient cohesive force and adhesive force, adhesion to various substrates, stain resistance, durability, and resistance to yellowing as an adhesive composition. For this reason, the polymerizable composition or polymer thereof can be used as is as an adhesive composition. On the other hand, by crosslinking the adhesive composition containing the polymerizable composition or polymer thereof using the crosslinking methods (1) to (3) described above with the crosslinking agent, an adhesive composition with even better stain resistance and durability can be obtained.

[0064] The adhesive composition according to the fifth embodiment can be used as an adhesive layer after being applied to or molded onto a separator or substrate. Alternatively, it can be used as an active energy ray and / or thermosetting adhesive composition, which forms an adhesive layer by curing with active energy rays and / or heat. Furthermore, if the adhesive composition contains an organic solvent, it is dried at a temperature of 60 to 120°C for 1 to 30 minutes after being applied to or molded onto the separator or substrate. Conventional known methods can be used to apply the adhesive composition to the separator or substrate, such as spin coating, spray coating, knife coating, dipping, gravure roll, reverse roll, screen printing, and bar coater methods.

[0065] A laminate is obtained by laminating an adhesive layer made of the adhesive composition according to the fifth embodiment with various substrates. Methods for laminating the adhesive layer with various substrates include the transfer method and the roll-to-roll method. The thickness of the adhesive layer in the laminate is not particularly limited as it varies depending on the application, but is usually 4 μm to 150 μm, with about 20 μm to 120 μm being appropriate when used in automotive components, and about 30 μm to 100 μm being appropriate when used in electronic materials or optical components.

[0066] As substrates, various types can be used depending on the application, including organic substrates, inorganic substrates, and organic-inorganic composite materials, all possessing a wide range of polarities from low to high polarity. Examples of materials include polyolefins such as polyethylene and polypropylene, polyethylene terephthalate, polycarbonate, ABS resin (acrylonitrile-butadiene-styrene copolymer), acrylic resins such as polyimide, polyamide, and polymethyl methacrylate, metals such as steel, stainless steel, copper, and aluminum, glass, and hybrid materials in which silica nanoparticles (an inorganic material) are dispersed in polyimide (an organic material). The applications of these various substrates are not particularly limited, but examples include applications for electronic materials, optical components, and automotive components.

[0067] The adhesive layer constituting the laminate according to the fifth embodiment is molded from a polymerizable composition containing N-substituted (meth)acrylamide (A) or a polymer thereof. N-substituted (meth)acrylamide (A) has a hydrophobic substituent that exhibits wettability to low-polarity substrates and a hydrophilic (meth)acrylamide group that exhibits wettability to high-polarity substrates in its molecule, thereby providing good adhesion from low-polarity to high-polarity substrates. Furthermore, by exhibiting strong cohesive force derived from hydrogen bonding between amide groups intermolecules of A, high adhesive strength and stain resistance can be provided. Moreover, since the polymerizable composition or polymer has high transparency and resistance to yellowing, the adhesive layer obtained therefrom also has high transparency and resistance to yellowing, and is suitably used in optical fields such as adhesives for optical components and adhesive sheets. Laminates consisting of such an adhesive layer and various substrates can be applied as adhesive films or adhesive sheets for electronic materials, optical components, and automotive components.

[0068] In the adhesive composition according to the fifth embodiment, the N-substituted (meth)acrylamide (A) in the adhesive composition can be introduced from a polymerizable composition containing A, and A can also be introduced as a structural unit from the polymer of the polymerizable composition and the polymer of N-substituted (meth)acrylamide (A). The total content of N-substituted (meth)acrylamide (A) and the structural units of A in the adhesive is preferably 0.1 to 90% by weight, more preferably 1 to 70% by weight, and particularly preferably 5 to 60% by weight, based on the total weight of the adhesive composition (excluding the solvent (the same applies hereinafter)). Furthermore, from the viewpoint of further improving wettability and adhesion to various substrates, the surface tension of N-substituted (meth)acrylamide (A) is 24.0 to 46.0 mN·m -1 It is preferable that this be the case.

[0069] In the adhesive composition according to the fifth embodiment, from the viewpoint of improving the water resistance of the adhesive layer formed using it, it is preferable that the polymerization initiator, the compound having an unsaturated bond, and the non-polymerizable components (including non-polymerizable oligomers, non-polymerizable polymers, and polymers according to the second embodiment of the present invention) further contained are hydrophobic. Also, in order to adjust the balance between hydrophilicity and hydrophobicity of the adhesive composition, the content of monofunctional monomers (excluding N-substituted (meth)acrylamide (A)) is preferably 10 to 90% by weight, more preferably 20 to 80% by weight, and particularly preferably 30 to 70% by weight, based on the total weight of the adhesive composition. The total content of crosslinking agents including polyfunctional monomers is preferably 1 to 30% by weight, more preferably 2 to 20% by weight, and particularly preferably 5 to 15% by weight, based on the total weight of the adhesive composition. The total content of non-polymerizable components is preferably 0.1 to 20% by weight, more preferably 0.5 to 15% by weight, and particularly preferably 1 to 10% by weight, based on the total weight of the adhesive composition. Such an adhesive composition exhibits high adhesion to various substrates, and the adhesive layer formed therefrom has high adhesive strength, excellent transparency, water resistance, stain resistance, yellowing resistance, and durability. Laminates of the adhesive layer made from the adhesive composition and various substrates can be obtained.

[0070] The sixth embodiment of the present invention is an adhesive composition (hereinafter also referred to as "adhesive"). The adhesive composition according to the sixth embodiment contains a polymerizable composition or polymer thereof according to the first to fourth embodiments and a crosslinking agent. Because the adhesive composition contains N-substituted (meth)acrylamide (A) and a crosslinking agent, it exhibits high adhesive strength and impact resistance to various substrates, such as organic substrates, inorganic substrates, and substrates made of organic-inorganic composite materials, which have a wide range of polarities from low to high polarity, and can therefore be used as an adhesive composition for the same or different materials.

[0071] Identical materials refer to materials of the same type among the various materials mentioned above, such as resins, metals, glass, and hybrid materials. Identical materials have a surface tension of 22.6 mN·m at 23°C. -1 ~59.0 mN·m -1 It is preferable that this is the case. If the same type of material has a surface tension within the above range, high adhesive strength can be obtained. The surface tension of each of the above materials at 23°C can be measured according to JIS K 6768, and the minimum surface tension that can be measured by this method is 22.6 mN·m. -1 In this specification, for the purpose of calculating the absolute value of the difference in surface tension between dissimilar materials, as described later, the surface tension value measured by this method is 22.6 mN·m. -1 The surface tension of the material below 22.6 mN·m -1 It is expressed as follows.

[0072] Dissimilar materials refer to materials of different types from the various materials mentioned above, such as resins, metals, glasses, and hybrid materials. The absolute difference in surface tension between the two dissimilar materials bonded via the adhesive composition at 23°C is 37.0 mN·m. -1 The following is preferable: Since dissimilar materials may have the same surface tension even if they are different materials, the absolute value of the difference in surface tension should be 0.0 mN·m -1 That concludes the explanation. Good adhesion can be obtained if the absolute value of the difference in surface tension of the dissimilar materials falls within the aforementioned range.

[0073] In the adhesive composition according to the sixth embodiment, the N-substituted (meth)acrylamide (A) in the adhesive composition can be introduced from a polymerizable composition containing A, and A can also be introduced as a structural unit from the polymer of the polymerizable composition and the polymer of N-substituted (meth)acrylamide (A). The total content of N-substituted (meth)acrylamide (A) and the structural units of A in the adhesive is preferably 1 to 95% by weight, more preferably 10 to 85% by weight, and particularly preferably 2 to 80% by weight, based on the total weight of the adhesive (excluding the solvent). Furthermore, from the viewpoint of further improving the adhesive strength between similar materials and between different materials, the surface tension of N-substituted (meth)acrylamide (A) is 24.0 to 46.0 mN·m -1 It is preferable that this be the case.

[0074] In the adhesive composition according to the sixth embodiment, from the viewpoint of improving the water resistance of the cured product obtained by curing using the same, it is preferable that the polymerization initiator, the compound having an unsaturated bond, and the non-polymerizable component (including non-polymerizable oligomers, non-polymerizable polymers, and polymers according to the second embodiment of the present invention) further contained are hydrophobic. Furthermore, in order to adjust the balance between hydrophilicity and hydrophobicity of the adhesive composition and improve the cohesive force, the content of monofunctional monomers (excluding N-substituted (meth)acrylamide (A)) is preferably 1 to 85% by weight, more preferably 2 to 80% by weight, and particularly preferably 5 to 75% by weight, based on the total weight of the adhesive composition. Moreover, the content of (meth)acrylate monomers as monofunctional monomers is most preferably less than 50% by weight in order to sufficiently maintain the cohesive force derived from (meth)acrylamide monomers.

[0075] In the adhesive composition according to the sixth embodiment, the total content of the crosslinking agent containing polyfunctional monomers is preferably 1 to 50% by weight, more preferably 5 to 30% by weight, and particularly preferably 10 to 25% by weight, based on the total weight of the adhesive composition. If the content is less than 1% by weight, the crosslinking by the crosslinking agent will be insufficient, resulting in insufficient cohesive force of the adhesive and insufficient impact resistance and heat resistance. On the other hand, if the content exceeds 50% by weight, the crosslink density of the adhesive after crosslinking is too high, which tends to reduce adhesion to the substrate due to shrinkage, resulting in a decrease in adhesive strength. The crosslinking reaction using the crosslinking agent can be carried out by the crosslinking methods (1) to (3) described above. Furthermore, the total content of non-polymerizable components is preferably 0.01 to 15% by weight, more preferably 0.1 to 10% by weight, and particularly preferably 0.5 to 8% by weight, based on the total weight of the adhesive composition. Such adhesive compositions have high adhesive strength, impact resistance, and water resistance to various substrates and are suitably used for bonding the same or different materials. Furthermore, the N-substituted (meth)acrylamide (A) used in the invention has high resistance to yellowing, and the adhesive composition according to the sixth embodiment can also be used as an adhesive for optical film laminates such as phase difference films and polarizing plates.

[0076] The seventh embodiment of the present invention is a cosmetic composition (hereinafter also referred to as "cosmetic composition"). The cosmetic composition according to the seventh embodiment contains a polymerizable composition or polymer thereof according to the first to fourth embodiments. The cosmetic composition can be used as a cosmetic composition having moisture resistance by containing N-substituted (meth)acrylamide (A). It can also be used as a cosmetic composition having emulsion stability due to the well-balanced amphiphilicity of N-substituted (meth)acrylamide (A). From the viewpoint of improving moisture resistance and emulsion stability, the surface tension of N-substituted (meth)acrylamide (A) is 24.0 to 46.0 mN·m -1 It is preferable that this be the case.

[0077] The cosmetic composition according to the seventh embodiment may further contain other components depending on the use and dosage form, and the other components are not particularly limited. For example, when the cosmetic composition is used as a skin cosmetic, other components may include various polymerization initiators, polyalkylene oxide macromonomers such as polyethylene oxide macromonomers, hydrocarbon oils for producing oil-in-water emulsion cosmetics, higher fatty acids, higher alcohols, synthetic ester oils, silicone oils, liquid oils and fats, solid oils and fats, waxes, fragrances and other oil-phase components, and aqueous-phase components such as water, water-soluble alcohols, and thickeners. Furthermore, when the cosmetic composition is used as a hair cosmetic in the form of a hair spray, other components may include polymerization initiators, high molecular weight surfactants, basic compounds, etc. In particular, by using tert-octylacrylamide, tert-butylacrylamide, etc., the solubility of the cosmetic composition in LPG (liquefied petroleum gas) is improved, and it can be suitably used (tert-octylacrylamide) or used in combination (tert-butylacrylamide) in aerosol products such as hair sprays that use LPG as a hair cosmetic.

[0078] In the cosmetic composition according to the seventh embodiment, the N-substituted (meth)acrylamide (A) in the cosmetic composition can be introduced from a polymerizable composition containing A, and A can also be introduced as a structural unit from the polymer of the polymerizable composition and the polymer of N-substituted (meth)acrylamide (A). The total content of N-substituted (meth)acrylamide (A) and the structural units of A in the cosmetic composition is preferably 1 to 80% by weight, more preferably 5 to 70% by weight, and particularly preferably 10 to 60% by weight, based on the total weight of the cosmetic composition. Such a cosmetic composition does not cause skin irritation, has moisture resistance, emulsification stability and aging stability, and has excellent usability such as smoothness, resistance to stickiness, texture, richness, and quick absorption.

[0079] The eighth embodiment of the present invention is a coating agent composition (hereinafter also referred to as the coating agent). The coating agent composition according to the eighth embodiment contains the polymerizable composition or polymer thereof according to the first to fourth embodiments. The coating agent composition contains N-substituted (meth)acrylamide (A), and has high wettability to various substrates, such as organic substrates, inorganic substrates, and substrates made of organic-inorganic composite materials, which have a wide range of polarities from low to high. A conventionally known method can be used to apply the coating agent composition to the substrate. After being applied to the substrate, the coating agent composition is cured by the aforementioned active energy rays and / or heat. The thickness of the coating agent composition applied to the substrate is not particularly limited, but it is preferably a thickness that allows for sufficient curing by active energy rays and / or heat, and is generally 1 to 100 μm. The resulting cured product (coating layer) has adhesion to the aforementioned various substrates and exhibits high pencil hardness and water resistance.

[0080] In the coating agent composition according to the eighth embodiment, the N-substituted (meth)acrylamide (A) in the coating agent composition can be introduced from a polymerizable composition containing A, and A can also be introduced as a structural unit from the polymer of the polymerizable composition and the polymer of N-substituted (meth)acrylamide (A). The total content of N-substituted (meth)acrylamide (A) and the structural units of A in the coating agent is preferably 1 to 80% by weight, more preferably 5 to 70% by weight, and particularly preferably 10 to 60% by weight, based on the total weight of the coating agent (excluding the solvent). Furthermore, from the viewpoint of improving adhesion to various substrates, the surface tension of N-substituted (meth)acrylamide (A) is 24.0 to 46.0 mN·m -1 It is preferable that this be the case.

[0081] The coating agent composition according to the eighth embodiment preferably further contains the crosslinking agent described above, in which case the pencil hardness and water resistance of the coating layer are improved. From this viewpoint, the content of the crosslinking agent in the total weight of the coating agent composition is preferably 5 to 70% by weight, more preferably 10 to 60% by weight, and particularly preferably 20 to 50% by weight. The coating agent composition may also contain the photopolymerization initiator, monofunctional monomers and oligomers, nonpolymerizable oligomers and polymers described above as other components. The content of the other components should be within a range that does not impair the aforementioned characteristics of the coating agent composition, and is usually 0.1 to 20 parts by weight per 100 parts by weight of the polymerizable composition. Such a coating agent composition has high wettability and adhesion to various substrates, and by using it, a coating film or other coating film that exhibits high surface hardness and water resistance when cured can be obtained.

[0082] The ninth embodiment of the present invention is an ink composition (hereinafter also referred to as "ink"). The ink composition according to the ninth embodiment contains a polymerizable composition or polymer thereof according to the first to fourth embodiments. The ink composition has high curability due to the inclusion of N-substituted (meth)acrylamide (A). A conventionally known method can be used to apply the ink composition to a substrate. The ink viscosity at 25°C is preferably less than 500 mPa·s, and more preferably less than 100 mPa·s from the viewpoint of being able to apply it to a substrate by an inkjet method. After being applied to the substrate, the ink composition is cured by the aforementioned active energy rays and / or heat to form an ink layer. From the viewpoint of further improving adhesion to various substrates, the surface tension of the N-substituted (meth)acrylamide (A) in the obtained ink layer is 24.0 to 46.0 mN·m -1 It is preferable that this be the case.

[0083] In the ink composition according to the ninth embodiment, the N-substituted (meth)acrylamide (A) in the ink composition can be introduced from a polymerizable composition containing A, and A can also be introduced as a structural unit from the polymer of the polymerizable composition and the polymer of N-substituted (meth)acrylamide (A). The total content of N-substituted (meth)acrylamide (A) and the structural units of A in the ink is preferably 5 to 90% by weight, more preferably 10 to 85% by weight, and particularly preferably 15 to 80% by weight, based on the total weight of the ink (excluding the solvent).

[0084] The ink composition according to the ninth embodiment may further contain the aforementioned crosslinking agent, in which case the curability, surface drying properties, and water resistance of the ink layer are improved. From these viewpoints, the content of the crosslinking agent in the total weight of the ink composition is preferably 1 to 50% by weight, more preferably 5 to 45% by weight, and particularly preferably 10 to 40% by weight. The ink composition may further contain the aforementioned photopolymerization initiator, monofunctional monomers and oligomers, nonpolymerizable oligomers and polymers as other components. The content of the other components should be within a range that does not impair the aforementioned characteristics of the ink composition, and is usually 0.1 to 30 parts by weight per 100 parts by weight of the polymerizable composition. Such an ink composition has high adhesion to various substrates, excellent printing properties such as pigment dispersibility, surface drying properties, ejection stability, and clarity, and by using it, an ink with high curability, resistance to yellowing, and water resistance can be obtained.

[0085] The tenth embodiment of the present invention is a three-dimensional printing ink composition. The three-dimensional printing ink composition according to the tenth embodiment contains a polymerizable composition or polymer thereof according to the first to fourth embodiments, or the polymerizable composition or polymer thereof and a crosslinking agent. Since the polymerizable composition or polymer thereof according to the first to fourth embodiments contains N-substituted (meth)acrylamide (A), the three-dimensional printing ink composition has high curability and resistance to curing shrinkage, and the cured product has high strength and water resistance and excellent molding accuracy. The three-dimensional printing ink composition is formed into a predetermined shape pattern and cured by irradiation with active energy rays and / or heat at the same time or immediately after formation to form a thin film, and a three-dimensional object is fabricated by stacking the thin films. The molding method is not particularly limited, but for example, a photopolymerization method in which the ink is ejected by an inkjet method and cured by irradiation with active energy rays can be mentioned. In this case, from the viewpoint of stable ejection, the viscosity of the three-dimensional printing ink composition at 25°C is preferably 1 to 200 mPa·s, and the ejection temperature is preferably in the range of 20 to 100°C. From the viewpoint of achieving a good appearance such as gloss and density in the resulting three-dimensional object, the surface tension of N-substituted (meth)acrylamide (A) should be 24.0 to 46.0 mN·m -1 It is preferable that this be the case.

[0086] In the three-dimensional printing ink composition according to the tenth embodiment, the N-substituted (meth)acrylamide (A) in the three-dimensional printing ink composition can be introduced from a polymerizable composition containing A, and A can also be introduced as a structural unit from the polymer of the polymerizable composition and the polymer of N-substituted (meth)acrylamide (A). The total content of N-substituted (meth)acrylamide (A) and the structural units of A in the three-dimensional printing ink composition is preferably 1 to 80% by weight, more preferably 2 to 70% by weight, and particularly preferably 5 to 60% by weight, based on the total weight of the three-dimensional printing ink.

[0087] The three-dimensional printing ink composition according to the tenth embodiment preferably further contains the aforementioned crosslinking agent, in which case three-dimensional objects with superior strength, water resistance, and heat resistance can be fabricated. From this viewpoint, the content of the crosslinking agent in the total weight of the three-dimensional printing ink composition is preferably 1 to 50% by weight, more preferably 5 to 40% by weight, and particularly preferably 10 to 30% by weight. Furthermore, the three-dimensional printing ink composition may further contain the aforementioned photopolymerization initiator, monofunctional monomers and oligomers, nonpolymerizable oligomers and polymers as other components. The content of the other components should be within a range that does not impair the aforementioned characteristics of the three-dimensional printing ink composition, and is usually 0.1 to 20 parts by weight per 100 parts by weight of the polymerizable composition. Three-dimensional objects with high strength, heat resistance, and water resistance can be fabricated with high precision from such a three-dimensional printing ink composition.

[0088] The polymerizable compositions according to the first to fourth embodiments may contain various additives other than those described above, as needed. Examples of additives include thermal polymerization inhibitors, antioxidants, ultraviolet sensitizers, preservatives, phosphate esters and other flame retardants, surfactants, antistatic agents, colorants such as pigments and dyes, fragrances, defoamers, fillers, silane coupling agents, surface tension modifiers, plasticizers, surface lubricants, leveling agents, softeners, organic fillers, inorganic fillers, silica particles, and the like. These additives may be used individually or in combination of two or more. The content of these additives is not particularly limited as long as it does not adversely affect the properties exhibited by the polymerizable composition or the various molded articles of its polymers, but it is preferably 5% by weight or less of the total weight of the polymerizable composition.

[0089] The various compositions according to the fifth to tenth embodiments may contain various additives other than those mentioned above, as needed. Examples of additives include thermal polymerization inhibitors, antioxidants, ultraviolet sensitizers, preservatives, phosphate esters and other flame retardants, surfactants, antistatic agents, colorants such as pigments and dyes, fragrances, defoamers, fillers, silane coupling agents, surface tension modifiers, plasticizers, surface lubricants, leveling agents, softeners, organic fillers, inorganic fillers, silica particles, and the like. These additives may be used individually or in combination of two or more. The content of these additives is not particularly limited as long as it does not adversely affect the properties exhibited by the various molded articles obtained from the various compositions, but it is preferably 30% by weight or less of the total weight of the composition. Furthermore, water, organic solvents, and mixtures thereof may be used as solvents or diluents as needed. The content of such solvents is not particularly limited as long as it does not adversely affect the properties exhibited by the various molded articles obtained from the various compositions, but it is preferably 95% by weight or less of the total weight of the composition. [Examples]

[0090] The present invention will be described in more detail below with reference to examples and comparative examples, but the present invention is not limited to the following examples. The abbreviations for each component described in the examples and comparative examples are as follows. In addition, unless otherwise specified, "parts" and "%" below are based on weight. (1) N-substituted (meth)acrylamide (A) CHAA: N-Cyclohexylacrylamide (registered trademark "Kohshylmer") (solid at room temperature, surface tension: 32.3 mN·m) -1 ) CHMAA: N-Cyclohexyl-N-methylacrylamide (registered trademark "Kohshylmer") (liquid at room temperature, surface tension: 32.5 mN·m) -1 ) ACP: N-Acryloylpiperidine (registered trademark "Kohshylmer") (liquid at room temperature, surface tension: 35.7 mN·m) -1 ) ACMP: N-Acryloyl-4-methylpiperidine (registered trademark "Kohshylmer") (liquid at room temperature, surface tension: 31.6 mN·m) -1 ) ACDMP: N-Acryloyl-3,5-dimethylpiperidine (registered trademark "Kohshylmer") (liquid at room temperature, surface tension: 28.6 mN·m) -1 ) NOAA: n-Octylacrylamide (registered trademark "Kohshylmer") (waxed state at room temperature, surface tension: 30.0 mN·m) -1 ) TOAA: tert-octylacrylamide (registered trademark "Kohshylmer") (solid at room temperature, surface tension: 29.1 mN·m) -1 ) EHAA: N-(2-ethylhexyl)acrylamide (registered trademark "Kohshylmer") (liquid at room temperature, surface tension: 29.7 mN·m) -1 ) DEHAA: N,N-di-2-ethylhexylacrylamide (registered trademark "Kohshylmer") (liquid at room temperature, surface tension: 31.0 mN·m) -1 ) LMAA: N-Lauryl methacrylamide (registered trademark "Kohshylmer") (Solid at room temperature, surface tension: 31.2 mN·m) -1 ) OLAA: N-Oleylacrylamide (registered trademark "Kohshylmer") (liquid at room temperature, surface tension: 32.3 mN·m) -1 ) STAA: N-Stearylacrylamide (registered trademark "Kohshylmer") (solid at room temperature, surface tension: 31.9 mN·m) -1 ) AAPB: 3-Acrylamide Phenylboronic Acid (Registered Trademark "Kohshylmer") (Solid at room temperature, surface tension: 24.0 mN·m) -1 ) DPAA: Dopamine acrylamide (registered trademark "Kohshylmer") (solid at room temperature, surface tension: 36.5 mN·m) -1 ) PHAM: Phenylacrylamide (registered trademark "Kohshylmer") (solid at room temperature, surface tension: 45.3 mN·m) -1 ) (2) Monofunctional monomers TBAA: tert-butylacrylamide BA: Butyl acrylate 2EHA:2-Ethylhexylacrylate STA: Stearyl acrylate OLA: Oleyl acrylate EA: Ethyl acrylate HEA: Hydroxyethyl acrylate 4HBA: 4-Hydroxybutyl acrylate PEA: Phenoxyethyl acrylate IBOA: Isobornyl acrylate THFA: Tetrahydrofurfurylacrylate AAc: Acrylic acid VOZO:2-Vinyl-2-Oxazoline (Registered trademark "Kohshylmer") MHAGE: N-methyl-N-hydroxyethylacrylamide glycidyl ether (registered trademark "Kohshylmer") GA: Glycidyl acrylate (registered trademark "Kohshylmer") "HEAA": Hydroxyethylacrylamide (Registered trademark "Kohshylmer", "HEAA") "DMAA": Dimethylacrylamide (Registered trademark "Kohshylmer", "DMAA") "DEAA": Diethylacrylamide (Registered trademarks "Kohshylmer" and "DEAA") "NIPAM": Isopropyl acrylamide (registered trademark "Kohshylmer", "NIPAM") DAAM: Diacetone acrylamide (registered trademark "Kohshylmer") (3) Polyfunctional monomers, etc. (polyfunctional monomers, oligomers) PETA: Pentaerythritol triacrylate DPHA: Dipentaerythritol hexaacrylate HDDA: 1,6-Hexanediol diacrylate TPGDA: Tripropylene glycol diacrylate UV-3000B: Bifunctional urethane acrylate (manufactured by Shiko and Mitsubishi Chemical Corporation) UV-6640B: Bifunctional urethane acrylate (manufactured by Shiko and Mitsubishi Chemical Corporation) Quick Cure 7100: UV-curable urethane oligomer (registered trademark "Quick Cure", manufactured by KJ Chemicals Co., Ltd.) Quick Cure 8100: UV-curable urethane oligomer (registered trademark "Quick Cure", manufactured by KJ Chemicals Co., Ltd.) (4) Others O-184: Omnirad 184 (photopolymerization initiator, manufactured by IGM Resins BV) O-1173: Omnirad 1173 (photopolymerization initiator, manufactured by IGM Resins BV) TPO: Omnirad TPO (photopolymerization initiator, manufactured by IGM Resins BV) HDI: Hexamethylene diisocyanate (crosslinking agent) HHPA: Hexahydrophthalic anhydride (crosslinking agent) AIBN: Azobisisobutyronitrile (radical polymerization initiator) V-601: Azobis(isobutyrate)dimethyl (radical polymerization initiator) KE-359: Hydrogenated rosin (Tackyfire, non-polymerizable polymer, manufactured by Arakawa Chemical Industries) VS-1063: Styrene acrylic resin (non-polymerizable oligomer, manufactured by Seikoh PMC Co., Ltd.) VS-1057: Acrylic resin (non-polymerizable polymer, manufactured by Seikoh PMC Co., Ltd.) 50HB-55: Polyoxyethylene(2) polyoxypropylene(2) butyl ether (m=2, n=2, molecular weight 240) (manufactured by Sanyo Chemical Industries, Ltd.) 50HB-100: Polyoxyethylene (5) polyoxypropylene (5) butyl ether (m=5, n=5, molecular weight 540) (manufactured by Sanyo Chemical Industries, Ltd.) 50HB-260: Polyoxyethylene (10) polyoxypropylene (7) butyl ether (m=10, n=7, molecular weight 880) (manufactured by Sanyo Chemical Industries, Ltd.) AMP:2-amino-2-methyl-1-propanol PME4000: Bremmer PME-4000 (manufactured by NOF Corporation) (5) Base material PE: Polyethylene sheet and film (Surface tension: 22.6 mN·m) -1 ) PP: Polypropylene sheet and film (Surface tension: 22.6 mN·m) -1 ) PC: Polycarbonate sheet and film (Surface tension: 34.0 mN·m) -1 ) ABS: Acrylonitrile-butadiene-styrene copolymer synthetic resin sheet (Surface tension: 34.0 mN·m) -1 ) PI: Polyimide sheets and films (Surface tension: 40.0 mN·m) -1 ) PMMA: Polymethyl methacrylate sheets and films (Surface tension: 36.0 mN·m) -1 ) PET: Easy-to-adhere polyethylene tereflat sheet and film (surface tension: 59.0 mN·m) -1 ) SPCC: Cold-rolled steel sheet (Surface tension: 45.0 mN·m) -1 ) SST: Stainless steel plate (Surface tension: 40.0 mN·m) -1 ) Cu: Copper plate (Surface tension: 38.0mN m -1 ) Al: Aluminum plate (Surface tension: 36.0 mN·m) -1 ) GL: Transparent glass plate (Surface tension: 40.0 mN·m) -1 ) PI-Silica: Silica fine particle dispersion polyimide plate and film (Surface tension: 40.0 mN·m) -1 )

[0091] Example 1 (Preparation and evaluation of polymers of N-substituted (meth)acrylamide (A)) In a 500 mL flask equipped with a thermometer, stirrer, reflux condenser, and nitrogen inlet tube, 30 g of CHAA, 44 g of 2EHA, 20 g of "NIPAM", 5 g of HEA, 1 g of AIBN as N-substituted (meth)acrylamide (A), and 100 g of ethyl acetate as a solvent were added. After homogeneous mixing at room temperature, nitrogen purging was performed for 30 minutes, and the reaction mixture was heated to 70°C and the polymerization reaction was carried out for 8 hours. After the reaction was complete, ethyl acetate was added to the reaction mixture to prepare a polymer solution with a solid content of 30%. The viscosity of the polymer solution at 25°C was measured using a cone-plate viscometer (RE550 model, manufactured by Toki Sangyo Co., Ltd.) in accordance with JIS K5600-2-3 and was found to be 4250 mPa·s. Furthermore, 30 g was taken from the polymer solution and the polymer was obtained by completely removing the volatile components from the solution. Subsequently, the obtained polymer was dissolved in tetrahydrofuran (THF) to prepare a 0.5 wt% THF solution of the polymer, which was allowed to stand overnight. The THF solution of the polymer was then filtered through a 0.45 μm membrane filter, and gel permeation chromatography (GPC) was performed using the filtrate (Shimadzu Prominence GPC system, Shodex KF-806L column, eluent THF). Based on the polystyrene equivalent, the weight-average molecular weight (Mw) of the polymer was calculated to be 960,000.

[0092] (Evaluation of the water resistance of polymers) Similarly, 30 g was taken from the polymer solution, volatile components were completely removed from the solution, and the polymer was dried under vacuum at 60°C for 24 hours to obtain a dry polymer. Then, 5 g of the dry polymer was accurately weighed using a plastic petri dish (weighed) to obtain the weight of the polymer in its dry state. The petri dish containing the polymer was placed in a constant temperature and humidity chamber and subjected to conditions of 30°C and 90% humidity for 24 hours and 48 hours. After removing it from the chamber, the weight was weighed to confirm that the polymer had reached saturation water absorption, and this was recorded as the weight of the polymer in its saturation water absorption state. The saturation water absorption rate was calculated according to the following formula, and the water resistance of the polymer was evaluated in four stages as shown below. The results are shown in Table 1. Saturation water absorption rate (%) = (Weight in saturated water state - Weight in dry state) / Weight in dry state × 100% ◎: The saturation water absorption rate is 5% or higher. ○: The saturated water absorption rate is greater than 5%, but less than or equal to 7%. △: The saturation water absorption rate is over 7%, but less than 10%. ×: The saturation water absorption rate exceeds 10%.

[0093] Examples 2-12 and Comparative Examples 1-3 (Production of polymers of N-substituted (meth)acrylamide (A) and other polymers) The types and contents of N-substituted (meth)acrylamide, monofunctional monomer, and polymerization initiator were changed as shown in Table 1, and the polymerization reactions of Examples 2-12 and Comparative Examples 1-3 were carried out in the same manner as in Example 1 to obtain polymer solutions with a solid content of 30%. The viscosity of the obtained polymer solutions and the molecular weight of the polymers were measured in the same manner as in Example 1, and the results are shown in Table 1.

[0094] [Table 1]

[0095] Examples 13-28 and Comparative Examples 4-7 (Preparation and Evaluation of Polymerizable Compositions) The N-substituted (meth)acrylamide (A) and other components used in this embodiment were weighed in proportion to those shown in Table 2 and uniformly mixed at room temperature to prepare the polymerizable compositions of the examples and comparative examples. The transparency and wettability of the obtained polymerizable compositions to various substrates were evaluated by the following method, and the results are shown in Table 2. The polymerizable compositions of Examples 15, 16, 18 and 21 are polymerizable resin compositions for thermal polymerization, and are Examples 4, 2, 8 and 3 shown in Table 1, respectively, and the properties of their polymers are shown in Table 1. The polymerizable resin compositions other than those for thermal polymerization are polymerizable resin compositions for active energy ray curing, and the curability and water resistance of the obtained cured products were evaluated by the following method, and the results are shown in Table 2. Note that Example 14 is a method of curing by irradiation with an electron beam (EB) instead of ultraviolet light. A Curetron EBC-200-AA3 manufactured by Nissin High Voltage Co., Ltd. was used as the EB irradiation device (acceleration voltage: 200kV, irradiation dose: 20kGy).

[0096] [Table 2]

[0097] (Transparency assessment) The various polymerizable compositions obtained were left to stand overnight at 23°C, and their state was observed visually. Transparency was evaluated in four stages as described below. ◎: High transparency; no cloudiness or separation is observed at all. ○: High transparency, but slight cloudiness is visible. △: Layer separation is not observed, but the water is cloudy. ×: It is cloudy and further separated into layers.

[0098] (Wettability evaluation) The various polymerizable compositions obtained were applied to various substrates using a bar coater (RDS 3), and the wettability of the coating film was visually observed and evaluated in four stages as described below. ◎: The coating film is uniform and free from repellency. ○: There is a very slight amount of repellency, but the coating film is almost uniform. △: There is some repellency, but overall the coating film is fairly uniform. ×: The coating film is uneven and has many imperfections.

[0099] (Hardening evaluation) For curing, a 100 μm thick PET film (Toyobo Co., Ltd., polyester film Cosmoshine A4100) was placed on a horizontally positioned glass plate with its easy-adhesion side facing outwards. Using a bar coater No. 30, the polymerizable resin composition for active energy ray curing prepared in each example and comparative example was applied. A 50 μm thick light-release PET film (Toyobo Co., Ltd., polyester film E7002) was then placed on top, and ultraviolet light was irradiated at a predetermined cumulative light intensity (equipment: ITEC System Co., Ltd., desktop batch-type UV-LED curing device MUVBA-0.3×0.3×0.5, wavelength 405 nm, illuminance (UV-V) 50 mW / cm²). 2The resin composition was cured. Then, the release PET film was removed to obtain test pieces of cured material for curability evaluation for the examples and comparative examples. The tack of the surface of the obtained cured material was evaluated, and the following evaluation was performed using the cumulative light intensity at which the tack disappeared. ◎: Cumulative light intensity 200 mJ / cm 2 Tack disappears if less than ○: Total luminous intensity 200 mJ / cm 2 More than 500mJ / cm 2 Tack disappears if less than △: Total light intensity 500 mJ / cm 2 More than 1000mJ / cm 2 Tack disappears if less than ×: Tack disappears when the cumulative light intensity exceeds 1000 mJ / cm (including cases where tack does not disappear).

[0100] (Evaluation of the water resistance of the cured material) A silicone spacer (30mm x 15mm x 1mm) is placed on a glass plate (50mm x 50mm x 5mm thick), and the polymerizable resin composition for active energy ray curing prepared in each example and comparative example is poured into the spacer, followed by ultraviolet irradiation (700mW / cm²). 2 , 2000 mJ / cm 2 The material was cured using the following method to produce a cured sheet. The obtained sheet was cut into 3 cm squares and dried under vacuum at 60°C for 24 hours. The dried sheet was accurately weighed and recorded as the weight of the cured material in its dry state. The dried sheet was immersed in deionized water at 30°C, and after 24 hours and 48 hours, the weight was weighed immediately after removal from the deionized water to confirm that the sheet had reached saturation water absorption, and this was recorded as the weight of the cured material in its saturation water absorption state. The saturation water absorption rate was calculated according to the following formula, and the water resistance of the cured material was evaluated in four stages as described below. Saturation water absorption rate (%) = (Weight in saturated water state - Weight in dry state) / Weight in dry state × 100% ◎: The saturation water absorption rate is 5% or higher. ○: The saturated water absorption rate is greater than 5%, but less than or equal to 7%. △: The saturation water absorption rate is over 7%, but less than 10%. ×: The saturation water absorption rate exceeds 10%.

[0101] Examples 29-70 and Comparative Examples 8-20 (Preparation and Evaluation of Adhesive Compositions) (Examples 29-40 and Comparative Examples 8-10) Using the polymer solutions obtained in Examples 1-12 and Comparative Examples 1-3, heavy-release separators (silicone-coated PET films) were coated to a thickness of 25 μm after drying, and dried at 90°C for 2 minutes to form an adhesive layer. Next, the sheets were left in an environment of 23°C and 50% relative humidity for 1 day to obtain test adhesive sheets (type a-1). Furthermore, the type a test adhesive sheets from Examples 30, 35, 38 and Comparative Example 10 (those having unsaturated bonds derived from oleyl groups in the corresponding polymers) were irradiated with ultraviolet light (equipment: I-Graphics inverter-type conveyor system ECS-4011GX, metal halide lamp: I-Graphics M04-L41, ultraviolet irradiance: 700 mW / cm²). 2 Total luminous intensity: 1000 mJ / cm² 2 ) and a test adhesive sheet (type a-2) was obtained.

[0102] (Examples 41-48 and Comparative Example 11) The polymer solutions obtained in Examples 1, 4, 6, 8, and 12 and Comparative Example 1, along with HDI as a crosslinking agent, were weighed out to the solid content shown in Table 4 and uniformly mixed. As before, the mixture was applied to a PET film to a thickness of 25 μm after drying and dried at 90°C for 2 minutes to form an adhesive layer. Subsequently, it was aged in a 40°C constant temperature bath for 3 days, and then left in an environment of 23°C and 50% relative humidity for 1 day to obtain a test adhesive sheet (type b-1). In addition, the polymer solutions obtained in Examples 7, 9, and 10, along with polyacrylic acid (PAAc, manufactured by Fujifilm Wako Pure Chemical Industries, Ltd., average molecular weight 5,000) as a crosslinking agent, were weighed out to the solid content shown in Table 4 and uniformly mixed. As before, the mixture was applied to a PET film to a thickness of 25 μm after drying and dried at 90°C for 2 minutes to form an adhesive layer. Subsequently, the material was aged in a constant temperature chamber at 40°C for 3 days, and then left in an environment with a temperature of 23°C and a relative humidity of 50% for 1 day to obtain a test adhesive sheet (type b-2).

[0103] (Examples 49-53 and Comparative Examples 12 and 13) The polymer solutions obtained in Examples 2, 4, 5, 7, 8, and 11 and Comparative Examples 2 and 3 were weighed out, and monofunctional monomers, polyfunctional monomers and / or polyfunctional oligomers as crosslinking agents, photopolymerization initiators, and other components were weighed out in predetermined amounts as shown in Table 5 and uniformly mixed. As before, the mixture was applied to a PET film with a dry thickness of 25 μm and dried at 90°C for 2 minutes to form an adhesive layer. After that, ultraviolet light was irradiated (equipment: I-Graphics inverter-type conveyor device ECS-4011GX, metal halide lamp: I-Graphics M04-L41, ultraviolet irradiance: 700 mW / cm²). 2 Total luminous intensity: 1000 mJ / cm² 2 The material was then cured and left in an environment with a temperature of 23°C and a relative humidity of 50% for one day to obtain a test adhesive sheet (type c).

[0104] (Examples 54-65 and Comparative Examples 14-17) The polymerizable compositions obtained in Examples 13, 14, 17, 19, 20, 22-28 and Comparative Examples 4-7 were coated onto heavy-release separators (silicone-coated PET films), and then laminated with light-release separators (silicone-coated PET films) using a tabletop roll-type laminator (Royal Sovereign RSL-382S) to create an adhesive layer with a thickness of 25 μm, ensuring no air bubbles were trapped. The laminators were then irradiated with ultraviolet light (equipment: iGraphics inverter-type conveyor system ECS-4011GX, metal halide lamp: iGraphics M04-L41, ultraviolet irradiance: 700 mW / cm²). 2 Total luminous intensity: 1000 mJ / cm² 2 A transparent adhesive sheet for optical use (type d) was fabricated.

[0105] (Examples 66-72 and Comparative Examples 18-20) The polymer solutions or polymerizable compositions obtained in Examples 1, 6, 8, 12-14, 19, and 24, and Comparative Examples 1, 4, and 5, along with HDI or polyfunctional monomers and / or polyfunctional oligomers as crosslinking agents, photopolymerization initiators, and other components were weighed out in predetermined amounts as shown in Table 7 and uniformly mixed. Adhesive sheets were prepared in the same manner as in Type c (when polymers are used) or Type d (when polymerizable compositions are used) and cured with ultraviolet light. Subsequently, the sheets were aged in a constant temperature bath at 40°C for 3 days, and then left in an environment at 23°C and 50% relative humidity for 1 day to obtain test adhesive sheets (Type e).

[0106] The properties of the various adhesive sheets produced were evaluated using the method described below, and the results are shown in Tables 3 to 7. (Transparency evaluation of adhesive sheets) The total light transmittance of the glass substrate was measured using a haze meter (NDH-2000, manufactured by Nippon Denshoku Industries Co., Ltd.) in accordance with JIS K 7105. Under conditions of 23°C and 50% relative humidity, the above adhesive layer was transferred to the glass substrate, and the total light transmittance of the glass substrate and the adhesive layer was measured. Subsequently, the transmittance of the glass plate was subtracted to calculate the transmittance of the adhesive layer itself, and the transparency was evaluated in four stages as described below. ◎: Transmittance is 90% or higher ○: Transmittance is 85% or higher and less than 90%. △: Transmittance is 50% or more, and less than 85%. ×: Transmittance is less than 50%

[0107] (Evaluation of adhesion) The activated energy ray-curable adhesive composition prepared above is coated onto various plate-shaped substrates (surfaces), and then laminated using a tabletop roll-type laminator (Royal Sovereign RSL-382S) with a light release separator (silicone-coated PET film) to a thickness of 5 μm, ensuring no air bubbles are trapped. Finally, ultraviolet light is irradiated (equipment: iGraphics inverter-type conveyor system ECS-4011GX, metal halide lamp: iGraphics M04-L41, ultraviolet irradiance: 700 mW / cm²). 2 Total luminous intensity: 2000 mJ / cm² 2) was done. After that, the light release separator was peeled off to obtain an adhesive sheet consisting of an adhesive layer and a substrate. Using the obtained adhesive sheet, 100 1 mm square grids were created in accordance with JIS K 5600, cellophane tape was attached to them, and the number of grids on which the adhesive layer remained on the substrate side when peeled off in one go was counted, and the adhesion was evaluated according to the following criteria. ◎: 100 pieces, no peeling ○: No peeling with 95-99 pieces. △: 70-94 pieces, no peeling. ×: 0-69 pieces, no peeling.

[0108] (Evaluation of adhesive strength) Under conditions of 23°C and 50% relative humidity, the above adhesive layer was transferred to various film-like or plate-like substrates, and then pressed and attached using a 2kg pressure roller by two passes. The substrates were then left in the same atmosphere for 30 minutes. Subsequently, the 180° peel strength (N / 25mm) was measured using a tensile testing machine (device name: Tensilon RTA-100, manufactured by ORIENTEC) at a peeling speed of 300mm / min in accordance with JIS Z0237. ◎:30(N / 25mm) or more ○: 15 (N / 25mm) or more, less than 30 (N / 25mm) △: 8 (N / 25mm) or more, less than 15 (N / 25mm) ×: Less than 8 (N / 25mm)

[0109] (Stain resistance (reworkability) evaluation) In the same manner as the adhesive strength measurement described above, an adhesive sheet was prepared and left at 80°C for 24 hours. After peeling off the adhesive sheet, the contamination of the substrate film surface (residual state of the adhesive layer) was visually observed. ◎: No contamination (no adhesive residue). ○: There is a very slight contamination. △: Slight contamination present. ×: There is contamination (glue residue).

[0110] (Yellowing resistance evaluation) A sticky sheet was prepared in the same manner as the adhesive strength measurement described above, and it was set in a xenon fade meter (SC-700-WA: manufactured by Suga Test Instruments Co., Ltd.) to measure 70 mW / cm². 2 After irradiating the adhesive sheet with ultraviolet light of a certain intensity for 120 hours, the discoloration of the adhesive layer was visually observed. ◎: No yellowing is visible to the naked eye. ○: Very slight yellowing can be observed with the naked eye. △: Yellowing is visible to the naked eye. ×: Obvious yellowing is visible to the naked eye.

[0111] (Durability evaluation) Adhesive sheets were prepared in the same manner as described above for measuring adhesive strength, and after being held for 100 hours under conditions of 85°C and 85% relative humidity, the presence or absence of lifting, peeling, bubbles, or clouding of the adhesive layer was visually observed and evaluated. ◎: Transparent, no lifting, peeling, or air bubbles occur. ○: There is a very slight cloudiness, but no lifting, peeling, or air bubbles occur. △: Slight cloudiness, lifting, peeling, or air bubbles present. ×: There is extreme clouding, lifting, peeling, or air bubbles.

[0112] [Table 3]

[0113] [Table 4]

[0114] [Table 5]

[0115] [Table 6]

[0116] [Table 7]

[0117] Examples 73-82 and Comparative Examples 21-24 (Preparation and Evaluation of Adhesive Compositions) Polymers obtained in Examples 1-4, 6, 8, 9, 11 and Comparative Examples 1 and 2, and / or polymerizable compositions obtained in Examples 13, 14, 19, 20, 25-27 and Comparative Examples 4 and 5, along with crosslinking agents and other components, were weighed out to the solid content shown in Table 8 and uniformly mixed at room temperature to obtain a homogeneous mixture. Using two identical or different plate-shaped substrates measuring 100 mm (length) x 25 mm (width) x 1 mm (thickness), the mixture was uniformly applied to one of them. If the mixture contained a solvent, a generous amount of the mixture was applied so that the thickness after drying was similar to that of the solvent-free mixture, and it was dried at 90°C for 2 minutes. Then, in accordance with JIS K 6850, the other plate-shaped substrate was placed on top of the applied mixture, and the two substrates were bonded together so that the overlapping area was 12.5 mm (length) x 25 mm (width). The thickness of the adhesive layer was adjusted to 100 μm using a spacer, and a bonded test specimen was prepared. Subsequently, UV or EB irradiation was performed from the top surface of the bonded transparent or translucent substrate, in the same manner as in the preparation of the adhesive layer. In the examples where UV and EB are listed as the curing method in Table 8, the test specimens irradiated with UV rays and EB rays, respectively, were used as adhesive test specimens. In the examples where UV heat and EB heat are listed as the curing method, the test specimens irradiated with UV rays and EB rays, respectively, were further heated at 40°C for 72 hours, and the resulting test specimens were used as adhesive test specimens. In the examples where heat is listed as the curing method, the prepared test specimens were heated at 40°C for 72 hours without irradiation with either UV rays or EB rays, and the resulting test specimens were used as adhesive test specimens. Furthermore, the adhesive strength and impact resistance were evaluated using the obtained adhesive test specimens by the method described below, and the results are shown in Table 8.

[0118] (Adhesion strength evaluation) Using the obtained adhesive test specimens, the tensile shear strength was measured in accordance with JIS K 6850, using a Tensilon RTA-100 (manufactured by ORIENTEC) as the testing machine, under conditions of a tensile speed of 10 mm / min. ◎: Tensile shear strength is 20 MPa or higher. ○: Tensile shear strength is 15 MPa or more and less than 20 MPa. △: Tensile shear strength is 10 MPa or more and less than 15 MPa. ×: The tensile shear strength is less than 10 MPa.

[0119] (Impact resistance evaluation) Using the obtained adhesive test specimens, the impact peel adhesion strength was measured in accordance with JIS K6855 using an impact testing machine No. 511 (manufactured by Mize Testing Machine Co., Ltd.). ◎: Impact peel adhesion strength of 20 kJ / m 2 That's all. ○: Impact peel adhesion strength is 15 kJ / m 2 More than 20KJ / m 2 It is less than. △: Impact peel adhesion strength is 10 kJ / m 2 More than 15KJ / m 2 It is less than. ×: Impact peel adhesion strength is 10 kJ / m 2 It is less than.

[0120] [Table 8]

[0121] Examples 83-97 and Comparative Examples 25-28 (Production and Evaluation of Cosmetic Compositions) Examples 83-89 and Comparative Examples 25 and 26 (Manufacturing and Evaluation of Hair Cosmetic Compositions) 100 g of ethanol was added to a 1-liter four-necked flask equipped with a reflux condenser, thermometer, nitrogen displacement tube, and stirrer. Then, the polymer obtained in Table 1, the polymerizable composition obtained in Table 2, and other components were added in the proportions (solid content) shown in Table 9. The polymerization reaction was then carried out under reflux conditions (approximately 80°C) with a nitrogen stream for 8 hours. After the polymerization reaction was completed, 2-amino-2-methyl-1-propanol (AMP) (solid content), diluted with an equal amount of ethanol as a basic compound at 50°C, was added in the proportions shown in Table 9 to neutralize the mixture. The mixture was then further diluted with ethanol to obtain a base for hair cosmetics with a solid content of 40%. The obtained base for hair cosmetics, ethanol, and liquefied petroleum gas were mixed in a weight ratio of 7.5:42.5:50 and sealed in a spray can to obtain a hair spray type hair cosmetic. The moisture resistance, smoothness, resistance to stickiness, texture, and long-term stability of the obtained hair cosmetic composition were evaluated by the following method, and the results are shown in Table 9. Note that the polymerizable composition of Example 23 in Example 83 and the polymerizable composition of Example 28 in Example 84 were used without the polymerization initiator.

[0122] (Evaluation of set retention strength (moisture resistance) using the curl retention method) A hair bundle measuring 22 cm in length and weighing 2 g was sprayed with 0.4 g of the test formulation and spread evenly with a comb. This hair bundle was wrapped around a curler with a diameter of 2.2 cm and dried at 20°C for 20 hours. The hair bundle was then unwound in a spiral and mounted on a vertically positioned glass plate with markings. It was placed in a constant temperature and humidity chamber maintained at 30°C and 95% RH, and the position of the hair tips was recorded after 10 hours. Curl retention was calculated based on the following formula and evaluated according to the criteria below. Curl retention (%) = {(L-Lt) / (L-L0)} × 100 L: Length when the test hair is stretched out Lt: Position of the tip of the test hair after 10 hours of being left in a constant temperature and humidity chamber. L0: Position of the tip of the test hair before placing it in the constant temperature and humidity chamber. ◎: 80% or more ○: 65% or more and less than 80% △: 50% or more but less than 65% ×: Less than 50%

[0123] (Smoothness evaluation) A dry hair bundle measuring 22 cm in length and weighing 2 g was sprayed with the test formulation. Immediately after spraying and before drying (before drying), and after drying (after drying), an in-house monitor was able to untangle the hair bundle by hand and judged how easily it passed through, evaluating it according to the following criteria. ◎: There is no tackiness or squeaking before or after drying, and it has good glide. ○: It is smooth before drying, but after drying there is a slight tackiness and creaking. △: There is slight tackiness and stiffness before drying, and strong tackiness and stiffness after drying. ×: The fabric is too tucky and stiff before and after drying, making it unusable.

[0124] (Sticky resistance evaluation) Dry hair bundles were prepared, the test formula was sprayed onto them, and the stickiness of the dried hair bundles when held in the palm of the hand was evaluated. ◎: When touched with fingers, it feels smooth and not sticky. ○: It feels slightly sticky to the touch. △: It feels sticky to the touch. ×: When touched with fingers, it becomes sticky and difficult to remove from fingers.

[0125] (Texture evaluation) Similar to the moisture resistance evaluation, the feel of the prepared hair when touched by hand was evaluated using a sensory test conducted with in-house monitors, and the changes over time were also evaluated when the same test was performed one day later. The evaluation criteria are shown below. ◎: It was smooth and had a dry touch. ○: It was slightly stiff, but I was satisfied. △: Stiff or sticky. ×: It was quite stiff or very sticky.

[0126] (Evaluation of stability over time) After the above test formulation was left to stand at room temperature for one month, the degree of separation of the formulation components was observed visually and evaluated as follows. ◎: No separation occurred at all. ○: Slight separation was observed. After shaking for one minute and letting it stand for 7 days, no further separation occurred. △: Slight separation occurred, and redispersion was possible by shaking for 1 minute, but separation occurred again after 1 hour. ×: Separation occurred, and it was not possible to disperse it again even with the addition of shaking.

[0127] [Table 9]

[0128] Examples 90-97 and Comparative Examples 27, 28 (Production and Evaluation of Skin Cosmetic Compositions) 100 g of a water-ethanol mixed solvent (weight ratio 75:25) was added to a 1-liter three-necked flask equipped with a reflux tubing and a nitrogen inlet tube. The polymer obtained in Table 1, the polymerizable composition obtained in Table 2, and other components were added according to the proportions (on a solid content basis) shown in Table 10. After sufficient dissolution or dispersion, dissolved oxygen was removed by purging with nitrogen for 20 minutes. Then, the polymerization reaction was carried out in an oil bath at 65-70°C for 8 hours while stirring. After polymerization was complete, the dispersion obtained by returning the polymerization solution to room temperature was used as a raw material for cosmetics. 1 g of carboxyvinyl polymer and 0.6 g of potassium hydroxide, which are aqueous phase components, were added to deionized water and mixed. To this, 100 g of the aforementioned raw material for cosmetics, which had been dispersed separately in deionized water, was added and stirred. The total amount of deionized water used was 500 g. After uniformly dispersing the cosmetic raw materials and aqueous phase components, 100 parts liquid paraffin, 100 g of glycerin tri-2-ethylhexanoate, and dimethylpolysiloxane (6 cs) were added as oil phase components, and the mixture was sheared and mixed in a homomixer until homogeneous to obtain an oil-in-water emulsion cosmetic. The emulsion stability, skin irritation, feel, and long-term stability of the obtained oil-in-water emulsion cosmetic were evaluated by the following method, and the results are shown in Table 10. Note that the polymerizable composition of Example 13 in Example 90, the polymerizable composition of Example 17 in Example 91, the polymerizable composition of Example 19 in Example 95, and the polymerizable composition of Example 28 in Example 97 were used without the polymerization initiator.

[0129] (Emulsification stability (emulsified particle size) evaluation) The emulsified particles of the sample were observed using an optical microscope. ◎: The emulsified particles were uniform, and no coalescence or aggregation was observed. ○: The emulsified particles were almost uniform, but no coalescence or aggregation was observed. △: The emulsified particles were mostly uniform, but slight coalescence and aggregation were observed. ×: The emulsified particles were not uniform, and significant coalescence and aggregation were observed.

[0130] (Skin irritation test) Ten participants with sensitive skin had occlusive patches applied to the inner upper arm for 24 hours, and their skin condition was assessed according to the following criteria. 0... No abnormalities were found at all. 1…Slight redness is observed. 2…Redness is observed. 3…Redness and papules are observed. The evaluation criteria for the "skin irritation test" are as follows: ◎: The average value of the 10 panel members is between 0 and 0.15. ○: The average value of the 10 panel members is between 0.15 and less than 0.2. △: The average score of the 10 panel members is between 0.2 and 0.3. ×: The average value of the 10 panel members is 0.3 or higher.

[0131] (User experience evaluation) A panel of 10 experts evaluated the feel of the samples when applied to the skin ("non-stickiness," "richness," and "quick absorption") based on the following criteria. ◎: Seven or more people answered "Good" or "I can feel the difference." ○: Between 5 and 7 people answered "Good" or "I can feel the difference." △: 3 to 5 people answered "Good" or "I can feel the difference." ×: Two or fewer people answered "Good" or "I can feel the difference."

[0132] (Evaluation of stability over time) The state of the oil-in-water emulsion cosmetic product was observed visually one month after manufacturing. ◎: The sample maintains the emulsified state it was in during manufacturing. ○: Slight sedimentation / flotation is observed, but the sample remains largely emulsified. △: Emulsified particles settle / float, and particle coalescence is also observed. ×: The emulsified particles in the sample have settled / floated and coalesced, resulting in complete separation of the oil phase.

[0133] [Table 10]

[0134] Examples 98-105 and Comparative Examples 29 and 30 (Preparation and Evaluation of Coating Compositions) According to the proportions listed in Table 11 (based on solid content), the polymers obtained in Table 1, the polymerizable compositions obtained in Table 2, and other components were weighed and uniformly mixed at room temperature to prepare the coating agent composition. Coating test pieces (coating films) were prepared using the method described below, and the wettability, pencil hardness, and adhesion of the coating films to various substrates were evaluated. The results are shown in Table 11.

[0135] (Preparation of coating test specimens (coating films)) The coating agent composition was dropped in a strip onto the leading edge of various substrates (surfaces), applied with a bar coater (RDS 3), and dried at 90°C for 2 minutes. Then, curing was performed using the curing methods shown in Table 11 (UV, EB, heat, UV heat, EB heat) to form a coating layer on the substrate. Next, the samples were left in an environment of 23°C and 50% relative humidity for 1 day to obtain coating test pieces for evaluation. For the UV curing method, ultraviolet light was irradiated with the coated surface facing upwards (Equipment: I-Graphics inverter-type conveyor device ECS-4011GX, metal halide lamp: I-Graphics M04-L41, UV irradiance: 700 mW / cm²). 2 Total luminous intensity: 1000 mJ / cm² 2UV curing is a method of curing by irradiating with an electron beam instead of ultraviolet light. As the EB irradiation device, we used the Curetron EBC-200-AA3 manufactured by Nisshin High Voltage Co., Ltd. (acceleration voltage: 200kV, irradiation dose: 20kGy). UV curing is a method in which, after UV curing, aging is performed for 72 hours at 40°C to complete the crosslinking reaction by the crosslinking agent. EB curing is a method in which, after EB curing, aging is performed for 72 hours at 40°C to complete the crosslinking reaction by the crosslinking agent.

[0136] (Evaluation of the wettability of coating compositions) The coating composition was applied to various substrates using a bar coater (RDS 3), and the degree of coating liquid repellency was observed visually. ◎: The coating film is uniform and free from repellency. ○: There is a very slight amount of repellency, but the coating film is almost uniform. △: There is some repellency, but overall the coating film is fairly uniform. ×: The coating film is uneven and has many imperfections.

[0137] (Pencil hardness evaluation) The evaluation was based on JIS K 5400 8.4 Manual scraping method (1990 edition).

[0138] (Evaluation of adhesion) In accordance with JIS K 5600, 100 1mm square grids were created, cellophane tape was applied to them, and the number of grids on the substrate that retained adhesive after being peeled off in one go was counted, and the adhesion was evaluated according to the following criteria. ◎: 100 pieces, no peeling ○: No peeling with 95-99 pieces. △: 70-94 pieces, no peeling. ×: 0-69 pieces, no peeling.

[0139] [Table 11]

[0140] Examples 106-113 and Comparative Examples 31-33 In accordance with the proportions listed in Table 12 (based on solid content), the polymers obtained in Table 1, the polymerizable compositions obtained in Table 2, and other components were weighed and uniformly mixed at room temperature to prepare the ink compositions. The viscosity of the prepared ink compositions was measured to evaluate the dispersibility of the raw materials. Furthermore, inkjet printing was performed using the prepared ink compositions, and the physical properties of the resulting printed materials were evaluated. For the clear ink compositions, no pigment or pigment dispersant was added. For the black ink compositions, the pigment Pignent Black 7 was added, and evaluations were conducted for both compositions with and without the pigment dispersant Adisper PB821. The evaluation results are summarized in Table 12.

[0141] (Viscosity measurement and evaluation) The viscosity of the ink composition was measured in accordance with JIS K5600-2-3 using a cone-plate viscometer (RE550 viscometer manufactured by Toki Sangyo Co., Ltd.). For inkjet printing ink compositions, the viscosity was evaluated in four stages as follows. ◎: Less than 5-100 mPa·s ○: Less than 100-500 mPa·s △: Less than 500-2000 mPa·s ×:2000mPa·s or more

[0142] (Pigment dispersibility evaluation) The pigment aggregation and sedimentation state of the prepared ink composition was visually observed immediately after preparation and after standing for two months, and the pigment dispersibility was evaluated in four stages as described below. ◎: No aggregation or precipitation of the pigment was observed immediately after preparation or after standing for two months. ○: No precipitation was observed immediately after preparation, but a slight pigment precipitate was observed after standing for 2 months. △: Immediately after preparation, slight aggregation and precipitation of the pigment were observed, but after standing for 2 months, clear aggregation and precipitation of the pigment were clearly seen. ×: Aggregation and precipitation of the pigment were clearly observed even immediately after preparation.

[0143] Method for producing printed materials using ultraviolet irradiation The obtained ink composition was applied to a PET film with a thickness of 100 μm using a bar coater (RDS12) (film thickness after drying: 10 μm), and then cured by ultraviolet irradiation (using an inverter conveyor device ECS-4011GX manufactured by Eye Graphics Co., Ltd. and a metal halide lamp M04-L41) to produce a printed matter.

[0144] (Curing property evaluation) When producing a printed matter by the above method, the integrated light amount until the ink composition was completely cured (non-sticky state) was measured to evaluate the curing property. ◎: Completely cured at 1000 mJ / cm 2 ​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​) It was completely cured. The obtained cured film was subjected to a checkerboard test method to create 100 squares of 1 mm square, and cellophane tape was pasted on it. When it was peeled off at once, the number of squares with the cured film remaining on the substrate side was counted and evaluated. ◎: Number of remaining squares: 100 〇: Number of remaining squares: 90 or more and less than 100 △: Number of remaining squares: 50 or more and less than 90 ×: Number of remaining squares: less than 50

[0147] (Inkjet printing and printing suitability evaluation) The ink composition prepared above was filled into a commercially available inkjet printer (LuxelJet UV350GTW manufactured by Fujifilm Corporation), and a solid image was printed using coated paper, and the printing suitability of the ink was evaluated by the following method.

[0148] (Evaluation of ejection stability) The printing state of the obtained printed matter was visually evaluated. ◎: No nozzle clogging, printed well 〇: Slight nozzle clogging △: Nozzle clogging in a wide range ×: No ejection

[0149] (Evaluation of sharpness) The image sharpness of the printed matter obtained from the ink composition containing the pigment was visually observed. ◎: No bleeding of the ink was seen at all, and the image was sharp. ○: Almost no bleeding of the ink, and the image was good. △: Some bleeding of the ink was seen. ×:显著 bleeding of the ink was seen.

[0150] (Evaluation of yellowing resistance) The obtained clear ink composition was applied to a substrate (#125-E20) to a thickness of 10 μm using a bar coater (RDS12), and cured with a metal halide lamp in the same manner as described above. The hue of the obtained coating was measured using Spcetrolino (GretagMacbeth), and the film was left in a constant temperature bath maintained at 60°C for one week. After that, the hue of the coating was measured again, and the resistance to yellowing was evaluated by the change in hue value before and after heating (ΔE = hue after heating - hue before heating). ◎: 0 <= ΔE <= 0.2 ○: 0.2 < ΔE <= 0.5 △: 0.5 < ΔE <= 1.0 ×: 1.0 < ΔE

[0151] [Table 12]

[0152] Examples 114-122 and Comparative Examples 34, 35 According to the proportions listed in Table 13 (based on solid content), the polymers obtained in Table 1, the polymerizable compositions obtained in Table 2, and other components were weighed and uniformly mixed at room temperature to prepare a three-dimensional printing ink composition. The curing shrinkage rate of the three-dimensional printing ink composition and the strength, heat resistance, water resistance, and printing accuracy of the cured product of the three-dimensional printing ink composition were measured using the method described below. The evaluation results are shown in Table 13.

[0153] (Evaluation of resistance to hardening shrinkage) The curing shrinkage rate was determined according to JIS K5600 2-4, by the change in density before and after curing of the three-dimensional printing ink composition, as shown in the calculation formula (1) below. The density of the three-dimensional printing ink composition before and after curing was measured according to JIS K7112 using an electronic hydrometer (MDS-300 manufactured by Alpha Mirage Co., Ltd.). The cured material was prepared in the same manner as the test specimens used for the tensile test. The following evaluations were performed based on the obtained curing shrinkage rates. (Hardening shrinkage rate) = (Ds - Dl) / Dl × 100 ...Calculation formula (1) (In the formula, Ds is the density after curing of the three-dimensional shaping ink composition, and Dl is the density before curing of the three-dimensional shaping ink composition.) ◎: Curing shrinkage rate less than 6% ○: Curing shrinkage rate 6% or more and less than 7% △: Curing shrinkage rate 7% or more and less than 8% ×: Curing shrinkage rate 8% or more

[0154] (Strength evaluation) A heavy release PET film (manufactured by Toyobo Co., Ltd., polyester film E7001) with a thickness of 75 μm was adhered to a horizontally placed glass plate, a spacer with a thickness of 1 mm and punched into a No. 2 dumbbell shape conforming to JIS K6251 was installed, and the three-dimensional shaping ink compositions obtained in each example and comparative example were filled inside the spacer. Then, a light release PET film (manufactured by Toyobo Co., Ltd., polyester film E7002) with a thickness of 50 μm was overlaid thereon, and ultraviolet rays were irradiated from both sides (device: Inverter type conveyor device ECS-4011GX manufactured by Eye Graphics Co., Ltd., metal halide lamp: M04-L41 manufactured by Eye Graphics Co., Ltd., ultraviolet illuminance 200 mW / cm 2 , integrated light quantity 1000 mJ / cm 2 ) to cure the three-dimensional shaping ink composition. Then, the release PET films on both sides were removed to obtain test pieces of the cured product for the example and the cured product for the comparative example. According to JIS K7161, using a desktop precision universal testing machine (Autograph AGS-X manufactured by Shimadzu Corporation), the tensile strength was measured under the conditions of a temperature environment of 25°C, a tensile speed of 10 mm / min, and a chuck distance of 50 mm, and the strength was evaluated according to the criteria shown below.) ◎: Tensile strength 40 MPa or more ○: Tensile strength 30 MPa or more and less than 40 MPa △: Tensile strength 20 MPa or more and less than 30 MPa ×: Tensile strength less than 20 MPa

[0155] (Heat resistance evaluation) A cured material was prepared in the same manner as the specimen used for the tensile test described above, and its glass transition temperature (Tg) was measured using a differential scanning calorimeter (DSC-60plus, manufactured by Shimadzu Corporation). The heat resistance of the cured material was evaluated as follows based on the measured glass transition temperature (Tg). ◎: Cured product Tg 80℃ or more ○: Cured product Tg 40℃ or higher and less than 80℃ ×: Cured product Tg less than 40℃

[0156] (Water resistance evaluation) A 75μm thick heavy-release PET film (Toyobo Co., Ltd., polyester film E7001) was placed in close contact with a horizontally positioned glass plate. A 10mm thick spacer with an internal dimension of 10cm x 1cm was then placed inside the spacer. The three-dimensional molding ink compositions obtained in each example and comparative example were filled to a thickness of 1mm, and the surface was smoothed by heating at 60°C for 30 seconds. After that, ultraviolet light was irradiated (equipment: iGraphics inverter-type conveyor device ECS-4011GX, metal halide lamp: iGraphics M04-L41, ultraviolet irradiance 200mW / cm²). 2 The three-dimensional modeling ink composition was cured to obtain a cured object measuring 10 cm in length, 1 cm in width, and 1 mm in thickness. The weight of the obtained cured object was measured immediately after production, then immersed in a beaker containing 100 ml of water, and the weight after immersion was measured after one day. The water absorption rate was measured by substituting the weight before and after immersion into the following formula, and the water resistance was evaluated according to the criteria shown below. ◎: Water absorption rate is less than 2% ○: Water absorption rate of 2% or more and less than 2.5% △: Water absorption rate of 2.5% or more, but less than 3% ×: Water absorption rate of 3% or more

[0157] (Modeling accuracy evaluation) A 75-μm-thick peelable PET film (manufactured by Toyobo Co., Ltd., polyester film E7001) was adhered to a horizontally installed glass plate, a spacer with a thickness of 10 mm and an internal space of 10×10 mm was installed, and the three-dimensional shaping ink compositions obtained in each of the examples and comparative examples with a thickness of 1 mm were filled inside the spacer. After keeping it warm at 60°C for 30 seconds to smooth the surface, ultraviolet rays were irradiated (device: EC-4011GX, an inverter-type conveyor device manufactured by Eye Graphics, metal halide lamp: M04-L41 manufactured by Eye Graphics, ultraviolet illuminance 200 mW / cm 2 ) to cure the three-dimensional shaping ink compositions. Then, the filling and curing of the three-dimensional shaping ink compositions with a thickness of 1 mm were repeated a total of 10 times to obtain cured products of 10×10×10 mm. The height of the obtained cured products was measured. Also, the side surfaces of the obtained cured products were visually observed. Combining these results, the shaping accuracy was evaluated according to the following criteria.◎: The height is less than 10 mm ± 0.1 mm and there are no irregularities on the side surface. ○: The height is 10 mm ± 0.1 mm or more and less than ± 0.2 mm, or there are very slight irregularities on the side surface. △: The height is 10 mm ± 0.2 mm or more and less than ± 0.3 mm, or there are slight irregularities on the side surface. ×: The height is 10 mm ± 0.3 mm or more, or there are obvious irregularities on the side surface.

[0158]

Table 13

[0159] As shown in the evaluation results of the above-mentioned examples and comparative examples, the polymerizable composition containing N-substituted (meth)acrylamide (A) having a specific structure according to the present invention has high transparency and good curability due to the well-balanced amphiphilicity of A, and exhibits excellent wettability to various substrates having a wide range of polarities from low to high polarity, including organic substrates, inorganic substrates, and organic-inorganic hybrid substrates. Furthermore, the polymer or cured product exhibits excellent water resistance due to the hydrophobic substituents of A. The adhesive composition containing the polymerizable composition and / or its polymer, etc., and the laminate of an adhesive layer made from the adhesive composition and various substrates exhibit adhesion and tackiness to various substrates, and have high transparency, stain resistance, yellowing resistance, and durability. The adhesive composition containing the polymerizable composition and / or its polymer, etc., has high adhesive strength, impact resistance, and water resistance to various substrates and can be used as an adhesive composition for the same or different materials. The polymerizable composition and / or its polymers can be used as a hair cosmetic having moisture resistance, smoothness, non-stickiness, good texture, and long-term stability, or as an oil-in-water emulsion cosmetic composition that does not cause skin irritation and has excellent emulsification stability, feel, and long-term stability. The coating agent composition containing the polymerizable composition and / or its polymers has high wettability and adhesion to various substrates, and exhibits high surface hardness and water resistance upon curing. The ink composition has high adhesion to various substrates, excellent printing properties such as pigment dispersibility, surface drying properties, ejection stability, and clarity, and is clearly characterized by high curability and resistance to yellowing. Furthermore, the three-dimensional molding ink composition containing the polymerizable composition and / or its polymers can accurately mold three-dimensional objects with high strength, heat resistance, and water resistance. On the other hand, it is clear that various molded articles, such as adhesive compositions, cosmetic compositions, coating compositions, ink compositions, and three-dimensional molding ink compositions, obtained using polymerizable compositions and / or polymers thereof that do not contain N-substituted (meth)acrylamide (A), are inferior in effect to the various molded articles obtained from polymerizable compositions and / or polymers thereof that contain A. [Industrial applicability]

[0160] As described above, the polymerizable composition of the present invention, by containing a specific N-substituted (meth)acrylamide (A), possesses high transparency and good curability, while exhibiting excellent wettability to various substrates with a wide range of polarities from low to high, and its polymer has excellent water resistance. Therefore, the polymerizable composition and / or its polymer can be used as an adhesive composition that can be polymerized and cured by active energy rays and / or heat, in a wide range of fields such as industrial, medical, and household use, for adhesives and adhesive-related products. The adhesive composition has good adhesion to various substrates exhibiting a wide range of polarities. For example, by forming an adhesive layer on film-like or sheet-like substrates of polyolefins such as polyethylene and polypropylene, polycarbonate, acrylonitrile-butadiene-styrene copolymer, polyimide, and polymethyl methacrylate, polyolefin adhesive sheets and polyimide adhesive sheets can be obtained. Furthermore, when the adhesive layer is formed on a glass or metal substrate, glass adhesive sheets and metal adhesive sheets can be obtained. Furthermore, adhesive sheets for electronic materials comprising a substrate and adhesive layer for use in electronic devices, adhesive sheets for optical components comprising a substrate and adhesive layer for use in optical components, and adhesive sheets for automobiles comprising a substrate and adhesive layer for use in automobiles can be easily obtained. The adhesive composition comprising the adhesive composition and crosslinking agent of the present invention is very effective for bonding the same type of material as well as for bonding various dissimilar materials ranging from plastics to metals, and can be widely used in electronic materials, optical components, semiconductors, solar cells, etc. It can also be used in cosmetics with excellent moisture resistance and emulsification stability and a good feel, coating agents that can provide coating layers with excellent adhesion to various substrates and high surface hardness and water resistance, inks that have high adhesion to various substrates and excellent printing characteristics such as pigment dispersibility, surface drying properties, discharge stability, and clarity, and have high curability and resistance to yellowing, and inks for three-dimensional molding that have high strength, heat resistance and water resistance and excellent resistance to curing shrinkage that can accurately mold three-dimensional molded objects.

Claims

1. A polymerizable composition containing an N-substituted (meth)acrylamide (A) represented by general formula [1] and a monofunctional monomer (excluding (A)), or a coating agent composition containing a polymer obtained by polymerizing the polymerizable composition by active energy rays and / or heat, 【Chemistry 1】 (In the formula, R １ R represents a hydrogen atom or a methyl group. ２ and R ３ This indicates a structure in which these atoms, together with the supporting nitrogen atoms, form a saturated ring with six or more members. N-substituted (meth)acrylamide (A) is N-(meth)acryloylpiperidine, N-(meth)acryloyl-2-methylpiperidine, N-(meth)acryloyl-3-methylpiperidine, N-(meth)acryloyl-4-methylpiperidine, N-(meth)acryloyl-2,6-dimethylpiperidine, N-(meth)acryloyl-3,5-dimethylpiperidine, N-(meth)acryloyl-3,3-dimethylpiperidine, N-(meth)acryloyl-4,4-dimethylpiperidine, N-(meth)acryloyl-2,2,6,6-tetramethylpiperidine, N-(meth)acryloyl-2-methyl One or more compounds selected from the group consisting of N-5-ethylpiperidine, N-(meth)acryloyl-4-methyl-4-ethylpiperidine, N-(meth)acryloyl-2-ethylpiperidine, N-(meth)acryloyl-3-ethylpiperidine, N-(meth)acryloyl-4-ethylpiperidine, N-(meth)acryloyl-2-propylpiperidine, N-(meth)acryloyl-3-propylpiperidine, N-(meth)acryloyl-4-propylpiperidine, N-(meth)acryloyl-3-isopropylpiperidine, and N-(meth)acryloyl-4-isopropylpiperidine. A coating agent composition in which the content of (A) relative to the entire polymerizable composition is 1 to 90% by weight, and the content of the monofunctional monomer is 1 to 99% by mass.

2. The coating agent composition according to claim 1, wherein the monofunctional monomer is one or more compounds selected from the group consisting of monofunctional (meth)acrylate, monofunctional (meth)acrylamide other than N-substituted (meth)acrylamide (A), styrene, alkoxy group-containing monomer, vinyl group-containing monomer, allyl group-containing monomer, and maleimide group-containing monomer.

3. The coating agent composition according to claim 1 or 2, wherein the saturated water absorption rate of the polymer or cured product of the polymerizable composition is 10% or less.

4. A coating agent composition according to any one of claims 1 to 3, further comprising one or more compounds selected from the group consisting of polyfunctional monomers, monofunctional oligomers, nonpolymerizable oligomers, nonpolymerizable polymers (excluding polymers of N-substituted (meth)acrylamide (A)), crosslinking agents, and polymerization initiators.

5. The cured product of the coating agent composition according to claim 4, wherein the crosslinking agent is one or more compounds selected from the group consisting of hydroxyl group-containing (meth)acrylic monomers, carboxyl group-containing (meth)acrylic monomers, amino group-containing (meth)acrylic monomers, acetoacetyl group-containing (meth)acrylic monomers, isocyanate group-containing (meth)acrylic monomers, glycidyl group-containing (meth)acrylic monomers, oxazoline group-containing vinyl monomers, isocyanate compounds, epoxy compounds, aziridine compounds, and compounds having carboxyl and oxazoline groups.

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